A strength-improved copolymer and a method for preparing the same

Abstract

The application discloses a copolymer and a preparation method thereof, and belongs to the technical field of polymer synthesis. The copolymer comprises a polymer main body structure unit and a structure unit for improving the strength of the polymer, and the side chain group of the structure unit for improving the strength of the polymer contains an imide ring structure (R-0):(R-0), wherein R1 is a residue of an easy cyclization dibasic acid.

Description

A copolymer with improved strength and preparation method thereof Technical Field

[0001] The invention belongs to the technical field of polymer synthesis, in particular to a polyester copolymer with improved strength and a preparation method thereof. Background Art

[0002] Against the backdrop of continued global environmental deterioration and my country's "dual carbon" policy, the research and development and implementation of degradable alternatives to traditional resin materials have become key exploration topics in the resin industry. Currently, the improvement of the "degradability" of non-degradable resins is mainly achieved by blending easily degradable biomass. The final degradation performance of the material is essentially still derived from the biomass mixed in it, and the resin itself becomes non-degradable plastic particles after the material disintegrates, becoming a greater potential hidden danger affecting the environment and the health of animals and plants. From the long-term perspective of environmental protection, designing and synthesizing degradable materials at the molecular level has become the most effective means to solve plastic pollution.

[0003] Currently, mainstream biodegradable materials include PBS (polybutylene succinate), PLA (polylactic acid), and PBAT (copolymer of butylene adipate and terephthalate). PBS suffers from insufficient rigidity, a common drawback of aliphatic polyesters; PLA is highly crystalline, brittle, and intolerant to high and low temperatures; and PBAT offers excellent moldability but lacks rigidity. Therefore, those skilled in the art are in urgent need of designing biodegradable materials with adjustable and controllable mechanical properties to address these technical challenges. Summary of the Invention

[0004] In order to overcome the above technical deficiencies, the present invention provides a polyester copolymer with improved strength and a preparation method thereof, so as to solve the problems involved in the background technology.

[0005] In a first aspect, the present invention provides a copolymer comprising a polymer main structural unit and a structural unit for improving polymer strength, wherein the side chain group of the structural unit for improving polymer strength contains an imide ring structure (R-0):

[0006] Preferably, the structural unit for improving the strength of the polymer contains an imide ring structure represented by (RI); or further contains an open ring structure of an imide represented by (RI'):

[0007] X1 and X2 are O or N;

[0008] R1 is a residue of an easily cyclized dibasic acid, preferably at least one of an alkylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl, an alkylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl and is interrupted by one or more O atoms, an alkenylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a cycloalkylene group or a heterocycloalkyl group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a cycloalkenylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, an arylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a heteroarylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, or a bridged ring group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro;

[0009] Preferably, the alkylene group in the definition of R1 is C1-C 10 Alkylene, preferably C2-C6 alkylene, more preferably C2-C5 alkylene, most preferably ethylene, 1-methylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, 1,1,2,2-tetramethylethylene, 1-phenylethylene, 1-benzylethylene, 1,1-diphenylethylene, 1,1-dibenzylethylene, 1,2-diphenylethylene, 1,2-dibenzylethylene, propylene, 1-methylpropylene, 2-methylpropylene, 1,1-dimethylpropylene, 1,2-dimethylpropylene, 2,2-dimethylpropylene, 1,3-dimethylpropylene, 1-phenylpropylene, 2-phenylpropylene, 1,2-diphenylpropylene, 2,2-diphenylpropylene or 1,3-diphenylpropylene; the alkenylene in the definition of R1 is C2-C6 10 The alkenylene group is preferably a C2-C6 alkenylene group, more preferably a C2-C3 alkenylene group, and most preferably vinylene, 1-methylvinylene, 1,2-dimethylvinylene or propenylene group; the alkylene group in the definition of R1, which is unsubstituted or substituted by a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl, is interrupted by one or more O atoms and is interrupted by 1-3 oxygen atoms, such as 2-oxa-1,3-ethylene; the cycloalkylene group in the definition of R1 is a C3-C8 cycloalkylene group, preferably a C4-C6 cycloalkylene group, and most preferably a cyclobutylene or cyclohexylene group; the cycloalkenylene group in the definition of R1 can be a C4-C8 cycloalkenylene group, preferably a C4-C6 cycloalkenylene group, and most preferably a 3-cyclohexene-1,6-diyl group; the arylene group in the definition of R1 is a C6-C 10 Arylene, preferably phenylene, such as 1,6-phenylene; the cyclized group in the definition of R1 is norbornene;

[0010] R2 is a residue of a diol containing an amino group, preferably a trivalent alkyl group which is unsubstituted or substituted with a substituent selected from a halogen, an alkyl group or a nitro group, or at least one of a trivalent alkyl-aryl-alkyl group which is unsubstituted or substituted with a substituent selected from a halogen, an alkyl group or a nitro group;

[0011] Preferably, the trivalent alkyl-aryl-alkyl group in the definition of R2 is a trivalent C1-C 10 Alkyl-C6-C 10 Aryl-C1-C 10 Alkyl, preferably a trivalent C1-C5 alkyl-C6-C8 aryl-C1-C5 alkyl, more preferably a trivalent C1-C3 alkyl-C6-C8 aryl-C1-C3 alkyl,

[0012] Preferably, R2 is selected from at least one of the following structures:

[0013] In the above formula, * represents the bonding site with the O atom, and ** represents the bonding site with the N atom;

[0014] Further preferably:

[0015] R1 is selected from an alkylene group having 1 to 7 carbon atoms, preferably a linear or branched alkylene group having 1, 2, 3 or 4 carbon atoms in the main chain, an arylene group having 6 to 12 carbon atoms, a heteroalkylene group having 5 to 11 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, a heterocycloalkylene group having 2 to 11 carbon atoms or a combination thereof, optionally containing the following substituents: halogen, nitro, C 1-4 Alkyl, halogenated C 1-4 Alkyl, C 6-12 Aryl, C 6-12 Aryl-C 1-4 Alkyl or halogenated, C 1-4 Alkyl substituted C 6-12 Aryl or C 6-12 Aryl-C 1-4 alkyl;

[0016] R2 is selected from a linear alkylene group having 2 to 12 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, or a trivalent C1-C5 alkyl-C6-C8 aryl-C1-C5 alkyl group, optionally containing the following substituents: halogen, nitro, C 1-4 Alkyl, halogenated C 1-4 Alkyl, C 6-12 Aryl, C 6-12 Aryl-C 1-4 Alkyl or halogenated, C 1-4 Alkyl substituted C 6-12 Aryl or C 6-12 Aryl-C1-4 alkyl;

[0017] Most preferably:

[0018] R1 is a straight chain alkylene group having 2 or 3 carbon atoms in the main chain;

[0019] R2 is selected from a straight-chain alkylene group having 2 to 12 carbon atoms, a branched-chain alkylene group having 3 to 12 carbon atoms, a trivalent C1-C3 alkyl-C6-C8 aryl-C1-C3 alkyl group, a arylene group having 6 to 12 carbon atoms, or a cycloalkylene group having 3 to 12 carbon atoms.

[0020] In a specific embodiment of the present invention, the copolymer is at least one of a random copolymer, an alternating copolymer, a block copolymer and a graft copolymer of main chain structural units and structural units for improving polymer strength, preferably a random copolymer and / or a block copolymer.

[0021] In a specific embodiment of the present invention, the structural unit containing the (RI) structure is polyester, polyamide, polyurethane, polycarbonate or polyurea;

[0022] Preferably, it has the following structure:

[0023] X3 and X4 are N or O;

[0024] R3 is any divalent organic group;

[0025] Preferably, it is a residue of a dicarboxylic acid used for polymer synthesis, and is different from R1 and is a residue of any dicarboxylic acid, for example, it is a residue of a dicarboxylic acid that is easily cyclized as described in R1; or R3 is a residue of a dicarboxylic acid that is not easily cyclized, and the dicarboxylic acid that is not easily cyclized can be, for example, terephthalic acid or sebacic acid; Preferably, R3 is a chemical bond or an alkylene group that is unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl, ... at least one of an alkylene group substituted with a substituent, an alkenylene group unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a cycloalkylene group unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a cycloalkenylene group unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, an arylene group unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a heteroarylene group unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, or a bridged ring group unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro;

[0026] Preferably, R3 is selected from a linear or branched alkylene or alkenylene group having 2 to 12 carbon atoms, optionally interrupted by O atoms, an arylene group having 6 to 12 carbon atoms, a heteroarylene group having 5 to 11 carbon atoms, a cycloalkylene group, a cycloalkenyl group or a bridged cycloalkyl group having 3 to 12 carbon atoms, a heterocycloalkylene group having 2 to 11 carbon atoms, or a combination of the above groups, optionally containing the following substituents: halogen, C 1-4 Alkyl, halogenated C 1-4 Alkyl, C 6-12 Aryl, C 6-12 Aryl-C 1-4 Alkyl or halogenated, C 1-4 Alkyl substituted C 6-12 Aryl or C 6-12 Aryl-C 1-4 alkyl.

[0027] In a specific embodiment of the present invention, the structural unit containing (RI) is a polyester unit (R-IV);

[0028] R1, R2 or R3 is as described in claim 1 or 3.

[0029] In a specific embodiment of the present invention, the main structural unit is polyester, polyamide, polycarbonate, polyurethane or polyurea;

[0030] Preferably, the main structural unit is a polyester such as one or more of an aliphatic polyester, an aliphatic-aromatic polyester, and an aromatic polyester; further preferably, the main structural unit comprises two or more different structural units;

[0031] Preferably, it is a structural unit of one or more polyesters selected from PBS, PES, PBA, PET, PBT, PTT, PBAT, PBST, PEAT or PEST;

[0032] Preferably, the main structural unit of the copolymer and the structural unit that improves the strength of the polymer are both polyesters;

[0033] Preferably, R1 in the structural unit that improves the strength of the polymer is 3, i.e., 1,5-glutaric acid forms an imide heterocycle;

[0034] Preferably, R1 in the structural unit that improves the strength of the polymer is 2, that is, 1,4-butanedioic acid forms an imide heterocycle; preferably, the melt flow index of the copolymer is less than 130 g / 10 min, less than 100 g / 10 min, less than 80 g / 10 min, less than 50 g / 10 min, less than 20 g / 10 min, less than 15 g / 10 min, according to ASTM-D1238 standard.

[0035] In a specific embodiment of the present invention, the molar ratio of the structural unit for improving polymer strength to the main structural unit in the copolymer is 0.01 to 2.34, preferably 0.01 to 0.25.

[0036] In a specific embodiment of the present invention, the copolymer further comprises other modified structural units.

[0037] The second aspect of the present invention provides a polymer alloy comprising the copolymer according to the first aspect of the present invention.

[0038] The third aspect of the present invention is a polymer composition or a molded article comprising the copolymer according to the first aspect of the present invention or the polymer alloy according to the second aspect of the present invention.

[0039] The present invention also provides uses of the above-mentioned copolymer, the above-mentioned polymer alloy, or the above-mentioned composition or molded body, such as food containers, food packaging films, disposable tableware such as spoons or straws, transparent boxes for daily necessities, cosmetics, home appliances, etc., transparent windows of cardboard boxes and other packaging containers, transparent folders, document holders and other stationery, industrial films or agricultural films, clothing or industrial chemical fibers, etc.

[0040] The present invention also provides the use of a diol monomer represented by formula (II), a diol monomer containing an amide bond represented by formula (I), a precursor composition of a monomer represented by formula II or formula I, or a prepolymer formed from a monomer represented by formula II or I and a dicarboxylic acid used for polymer synthesis in preparing a copolymer with enhanced strength, wherein the copolymer has a tensile strength greater than 30 MPa;

[0041] Diol monomer represented by formula (II):

[0042] The diol monomer containing an amide bond shown in formula (I) is:

[0043] R1 and R2 are as defined in the first aspect of the present invention;

[0044] The precursor composition of the monomer of formula (II) or formula (I) is a primary amino diol and an easily cyclic dibasic acid and / or an acid anhydride corresponding to the dibasic acid, or a diol monomer containing an amide bond, wherein the primary amino diol is HOR2(NH2)OH.

[0045] The present invention also provides a method for preparing a copolymer, characterized by comprising:

[0046] A monomer composition is obtained by subjecting a primary amino diol to a cyclization reaction with a dibasic acid and / or an acid anhydride corresponding thereto to generate an imide;

[0047] Esterifying / transesterifying the monomer composition with a diol and a dibasic acid / ester to obtain a polyester copolymer containing a segment that improves polymer strength as shown in formula (III);

[0048] The chain segment that improves polymer strength has a structure shown in formula (III):

[0049] Wherein, m is any integer from 1 to 150;

[0050] In the formula, R1, R2 and R3 have the same meanings as those in the first aspect of the present invention.

[0051] In a specific embodiment of the present invention, the dibasic acid / ester is selected from one or more of aromatic dibasic acids / esters and aliphatic dibasic acids / esters.

[0052] In a specific embodiment of the present invention, the structural formula of the primary amino diol is shown in formula (IV):

[0053] Wherein, R2 is as defined above;

[0054] Preferably, the primary amino diol is one or more of 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-1-phenyl-1,3-propanediol, 4-amino-1,2-butanediol or 3,4-dihydroxyaniline.

[0055] In a specific embodiment of the present invention, the dibasic acid is a fatty acid terminal carboxyl dibasic acid having 3-9 carbon atoms; more preferably, it is a straight-chain or branched fatty acid terminal carboxyl dibasic acid having 4-6 main chain carbon atoms.

[0056] In a specific embodiment of the present invention, the monomer composition includes a diol monomer containing an imide cyclic structure;

[0057] The structural formula of the diol monomer containing an imide ring structure is shown in formula (II):

[0058] wherein R1 and R2 are as defined above.

[0059] In a specific embodiment of the present invention, the monomer composition includes a diol monomer containing an imide ring structure, a primary amino diol and / or a dibasic acid and / or an acid anhydride raw material corresponding to the dibasic acid, a diol monomer containing an amide bond, and a polyester prepolymer;

[0060] The structural formula of the diol monomer containing an imide ring structure is shown in formula (II):

[0061] wherein R1 and R2 are as defined above.

[0062] In a specific embodiment of the present invention, it is characterized in that the structural formula of the diol monomer containing an amide bond is as shown in formula (I):

[0063] wherein R1 and R2 are as defined in claim 1.

[0064] In a specific embodiment of the present invention, it is characterized in that the polyester prepolymer is a carboxyl-terminated prepolymer obtained by reacting a diol monomer containing an imide ring structure and / or a primary amino diol and / or a diol monomer containing an amide bond with an excess of a dibasic acid;

[0065] or

[0066] The polyester prepolymer is a hydroxyl-terminated prepolymer obtained by reacting an excessive amount of a diol monomer containing an imide ring structure and / or a primary amino diol and / or a diol monomer containing an amide bond with a dibasic acid.

[0067] In a specific embodiment of the present invention, it is characterized in that the molar ratio of the primary amino diol to the dibasic acid and / or its corresponding anhydride is 1:1.01-1:6.00.

[0068] In a specific embodiment of the present invention, the cyclization reaction to form imide comprises:

[0069] Adding a primary amino diol and a dibasic acid together, stirring and mixing, heating and melting, and performing an amidation reaction to obtain a diol containing an amide bond as shown in formula (I);

[0070] The diol containing an amide bond is continuously stirred under heat to undergo a thermal cyclization reaction to obtain a molten mixed solution containing a diol containing an imide cyclic structure as shown in formula (II), i.e., a monomer composition;

[0071] wherein R1 and R2 are as defined above.

[0072] In a specific embodiment of the present invention, the amidation reaction is carried out in a dry inert atmosphere that has been replaced with air, and a heat stabilizer and an antioxidant are added together with the primary amino diol and the dibasic acid;

[0073] Preferably, the thermal cyclization reaction temperature is 80-190° C., and the reaction time is 0.5-6 h.

[0074] In a specific embodiment of the present invention, the thermal cyclization reaction occurs under an inert atmosphere; preferably, the inert gas is nitrogen, and the flow rate of nitrogen in the thermal cyclization reaction system is >100 mL / min.

[0075] In a specific embodiment of the present invention, the total molar proportion of the polyester prepolymer obtained by reacting the diol monomer containing an imide ring structure and the diol monomer containing an amide bond in the monomer composition exceeds 80%, preferably exceeds 90%, and more preferably exceeds 95%.

[0076] The present invention relates to a copolymer and a preparation method thereof, which has the following beneficial effects compared with the prior art:

[0077] 1. The present invention provides a polyester material having a cyclic imide structure. The polyester material contains a cyclic imide structure and has the rigidity of an aliphatic ring structure. It is a degradable polyester with excellent mechanical properties.

[0078] 2. The cyclic imide modified composition provided by the present invention can be regulated by selecting different pre-primary amino diols and dibasic acid monomers to adjust the size of the imide ring, monomer rigidity and carbon chain type to meet the modification requirements of different types of polyesters.

[0079] 3. The polyester chain segment of the diol having a cyclic imide structure of the present invention is suitable for the thermal and mechanical properties of various traditional polyesters such as PBS, PES (polyethylene succinate), PBSA (polybutylene succinate-adipate), PBA (polybutylene adipate), PET (polyethylene terephthalate), PBT (polybutylene terephthalate), PTT (polypropylene terephthalate), PBAT (polybutylene terephthalate-adipate), PEAT (polyethylene terephthalate-adipate) or PEST (polyethylene terephthalate-succinate), etc., has a wide range of applications and has little effect on the color of the material. BRIEF DESCRIPTION OF THE DRAWINGS

[0080] FIG1 is a hydrogen nuclear magnetic spectrum (solvent: deuterated dimethyl sulfoxide) of the diol 2-succinimidyl propylene glycol obtained in Example 2 of the present invention.

[0081] FIG2 is a Fourier transform infrared spectrum (sample preparation by film coating method) of the diol obtained by 2-succinimide propylene glycol in Example 2 of the present invention.

[0082] FIG3 is a hydrogen nuclear magnetic spectrum (solvent: deuterated dimethyl sulfoxide) of the diol 2-cycloheximide propylene glycol obtained in Example 3 of the present invention. DETAILED DESCRIPTION

[0083] In the following description, numerous specific details are provided to provide a more thorough understanding of the present invention. However, it will be apparent to those skilled in the art that the present invention may be practiced without one or more of these details. In other instances, certain technical features well known in the art are not described to avoid confusion with the present invention.

[0084] The following describes the implementation of the present invention in detail with reference to the definitions of terms:

[0085] I. Diol Monomers Containing Imide Ring Structures and Their Synthesis

[0086] The present invention first provides a diol monomer containing an imide ring structure, wherein the monomer has the following structure:

[0087] In a specific embodiment of the present invention, the structural formula of the diol containing an imide ring structure is shown in formula (II-a to II-f):

[0088] In a further embodiment of the present invention, the diol containing an imide ring structure includes but is not limited to those shown in formulas (II-b-1 to II-b-8):

[0089] II. Structural units that increase polymer strength

[0090] In the present invention, the structural unit containing the structure (RI) contains a cyclic imide structure, which has the rigidity of the aliphatic ring structure, thereby improving the mechanical properties of the copolymer. In the present invention, the type of the structural unit is not limited in any way and can be selected from:

[0091] Polyester unit

[0092] In the present invention, preferably, the structural unit for improving the strength of the polymer is a polyester structure represented by formula (III):

[0093] Polycarbonate unit

[0094] In the present invention, the structural unit for improving polymer strength is preferably a polycarbonate structure represented by formula (RV):

[0095] Those skilled in the art are aware of the synthesis methods of polycarbonates, such as the phosgene method or the transesterification method, which synthesize the above-mentioned carbonates based on a diol monomer containing an imide ring structure (or its precursor or precursor composition), a diol (phenol) HO-R3-OH, and phosgene or an activated carbonate.

[0096] In a specific embodiment of the present invention, R3 is the same as R2 (and its imide ring substituent).

[0097] Polyurethane unit

[0098] It is also preferred in the present invention that the structural unit for improving polymer strength is a polyurethane structure represented by formula (R-VI):

[0099] Those skilled in the art are aware of the synthesis method of polyurethane, for example, polyurethane is obtained by reacting diisocyanate with a diol monomer containing an imide cyclic structure (or its precursor or precursor composition).

[0100] Polyamide structural unit or polyurea structural unit

[0101] In another embodiment of the present invention, a polyamide structural unit can be further obtained by converting a diol monomer containing an imide ring structure into a diamine:

[0102] Or polyurea structural unit:

[0103] The method of converting diol monomers into diamine monomers is well known in the field of organic chemistry, and the synthesis of polyamide structural units or polyurea structural units is well known in the field of polymers.

[0104] III. Copolymers with Enhanced Strength

[0105] In a specific embodiment of the present invention, the structural unit for improving polymer strength is introduced into the main structural unit in a manner of random copolymerization, block copolymerization, linear copolymerization or branched copolymerization to form a copolymer with improved strength.

[0106] In a specific embodiment of the present invention, the main structural unit of the copolymer is of a different type from the structural unit that increases the strength of the polymer.

[0107] In another specific embodiment of the present invention, the main chain structural units of the copolymer are of the same type as the structural units for improving the polymer strength, for example, both are polyester units, wherein the proportion of the structural units for improving the polymer strength to the total polyester units can be 0.5%-50%, or 1%-30%, or 2%-25%, or 3%-20%, preferably 5-15%.

[0108] In the specific embodiment of the present invention, polyester is taken as an example to illustrate the implementation of introducing structural units that improve polymer strength. Those skilled in the art can easily use similar methods to introduce them into other polymers.

[0109] Synthesis of polyester copolymers

[0110] The preparation method of the polyester copolymer of the present invention comprises:

[0111] Step 1: A primary amino diol is subjected to an amidation reaction with a dibasic acid and / or its corresponding acid anhydride to obtain a monomer composition; the monomer composition comprises a diol monomer containing an imide ring structure, wherein the diol monomer containing an imide ring structure is a main functional monomer. Specifically, the structural formula of the diol monomer containing an imide ring structure is shown in formula (II):

[0112] Step 2: subjecting the monomer composition to an esterification / transesterification reaction with a dibasic acid / ester to obtain a polyester copolymer comprising a segment for improving polymer strength as shown in formula (III); specifically, the copolymer comprises a segment for improving polymer strength and a polyester segment as the main polymer, wherein the segment for improving polymer strength has a structure as shown in formula (III):

[0113] Wherein, m is the number of repetitions of the segment, which is any integer from 1 to 150; preferably any integer from 2 to 50; specifically, the number of repetitions of the segment that improves polymer strength can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, or 150.

[0114] R1 is selected from an alkylene group having 1 to 7 carbon atoms, preferably a straight or branched alkylene group having 1, 2, 3 or 4 carbon atoms in the main chain; taking a diol containing an imide ring structure as an example, the structural formula of the diol containing an imide ring structure is shown in Formulas (II-a to II-f):

[0115] Taking the structure of the segment that improves the polymer strength as an example, the structure of the segment that improves the polymer strength is shown in formulas (III-a to III-f):

[0116] R2 is selected from a linear alkylene group having 2 to 12 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms, a substituted or unsubstituted arylene group having 6 to 12 carbon atoms, and a cycloalkylene group having 3 to 12 carbon atoms;

[0117] Taking R2 as a linear alkylene group having 2 carbon atoms as an example, the diol containing an imide ring structure includes but is not limited to those shown in formulas (II-b-1 to II-b-8):

[0118] Taking the segment structure for improving polymer strength as an example, the structure of the segment for improving polymer strength is shown in formulas (III-b-1 to III-b-8):

[0119] Since the diol monomer having a cyclic imide structure contains a cyclic imide structure, it has both the rigidity of the aliphatic ring structure and the degradability of the imide structure. It is a very convenient polyester chemical modification monomer that can enhance the mechanical properties of polyester polymers.

[0120] R3 is selected from a linear or branched alkylene group, an alkyleneoxy group, an arylene group, and a cycloalkylene group. When R3 is a reaction residue of a dibasic acid and / or a dibasic acid / ester, a person skilled in the art can reasonably select a dibasic acid, i.e., the structure of R3, based on the application requirements of the copolymer.

[0121] Among them, alkylene refers to the group remaining after formally removing two hydrogen atoms from an alkane molecule, and alkylidene refers to the group remaining after formally removing three hydrogen atoms from an alkane molecule; similarly, arylene refers to the group remaining after formally removing two hydrogen atoms from a benzene ring or a simple aromatic ring derivative, and arylene refers to the group remaining after formally removing three hydrogen atoms from a benzene ring or a simple aromatic ring derivative, cycloalkylene refers to the group remaining after formally removing two hydrogen atoms from a cycloalkane, and cycloalkylidene refers to the group remaining after formally removing three hydrogen atoms from a cycloalkane, and epoxy refers to the group remaining after formally removing two hydrogen atoms from an ether.

[0122] In a further embodiment, the dibasic acid / ester is selected from one or more of aromatic dibasic acids / esters and aliphatic dibasic acids / esters. Those skilled in the art will recognize that the preparation of polyester includes two pathways: esterification and transesterification. This application utilizes esterification as a synthetic method to prepare polyester, and those skilled in the art can readily infer that transesterification is a simple variation of esterification.

[0123] In a further embodiment, the polyester segment serving as the main polymer is a segment of a polyester selected from the group consisting of an aliphatic polyester, an aliphatic-aromatic polyester, and an aromatic polyester; and the molar ratio of the segment enhancing the polymer strength to the polyester segment serving as the main polymer is 0.01 to 2.34, preferably 0.01 to 0.25. In other words, the diol monomer having a cyclic imide structure of the present invention can be used to modify a variety of traditional polyesters, including but not limited to PBS, PES, PBA, PET, PBT, PTT, and PBAT, improving the thermal and mechanical properties of traditional polyester materials. It has a wide range of applications and minimal impact on the material's color.

[0124] In a further embodiment, the primary amino diol has a structural formula as shown in formula (IV):

[0125] In the formula, R2 is preferably a straight-chain alkylidene group having 2 to 12 carbon atoms, a branched-chain alkylidene group having 3 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms, or a cycloalkylidene group having 3 to 12 carbon atoms. The primary amino diol is one or more of 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-1-phenyl-1,3-propanediol, 4-amino-1,2-butanediol, 3,4-dihydroxyaniline, and 4-(2-aminoethyl)benzene-1,2-ethanediol. The dibasic acid is a fatty acid-terminated carboxyl-terminated dibasic acid having 3 to 9 carbon atoms; more preferably, the dibasic acid is a straight-chain or branched fatty acid-terminated carboxyl-terminated dibasic acid having 4 to 6 carbon atoms in the main chain.

[0126] During the preparation of the diol monomer having a cyclic imide structure in the present invention, various diol monomers with adjustable aliphatic carbon chains, controllable imide ring sizes and monomer rigidity can be synthesized through different pre-monomers to meet the modification requirements of different types of polyesters.

[0127] In a further embodiment, step 1 can be a one-step reaction or a step-by-step reaction. In the industrial production of polyester, reducing the production process and operation units and reducing the complexity of production and processing are of great significance for the stability of the product production process and the control of product quality. Preferably, the step-by-step reaction is adopted in the present invention to control the proportion of the imide ring structure in the monomer composition, improve the quality and stability of polyester synthesis, and obtain a high molecular weight polyester, for example, a polyester with a melt flow index of less than 140g / 10min, preferably less than 130g / 10min, less than 100g / 10min, less than 80g / 10min, less than 50g / 10min, less than 20g / 10min, and less than 15g / 10min. Specifically, the step 1 comprises: step 11, adding a primary amino diol and a dibasic acid together, stirring and mixing, heating and melting, and performing an amidation reaction to obtain a diol containing an amide bond as shown in formula (I); step 12, continuing to heat and stir the diol containing an amide bond under hot conditions to perform a thermal cyclization reaction to obtain a molten mixed solution containing a diol containing an imide ring structure as shown in formula (II), i.e., a monomer composition;

[0128] In the formula, R1 is a straight-chain alkylene group having 1 to 7 carbon atoms, preferably a straight-chain alkylene group having 1, 2, 3 or 4 carbon atoms;

[0129] R2 is selected from a linear alkylene group having 2 to 12 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms, a substituted or unsubstituted arylene group having 6 to 12 carbon atoms, and a cycloalkylene group having 3 to 12 carbon atoms.

[0130] In a further embodiment, the amidation reaction is carried out in a dry and air-replaced inert atmosphere, and a heat stabilizer and an antioxidant are added at the same time as the primary amino diol and the dibasic acid, and the concentration of the heat stabilizer and the antioxidant in the entire reaction system is 10-1000 ppm, respectively; preferably, the thermal cyclization reaction temperature is 80-190° C., and the reaction time is 0.5-6 h.

[0131] The thermal cyclization reaction is carried out under an inert atmosphere; preferably, the inert gas is nitrogen, and the flow rate of nitrogen in the thermal cyclization reaction system is >100 mL / min.

[0132] It is understood that the monomer composition includes a diol monomer containing an imide ring structure. For the monomer composition in this embodiment, it also includes a primary amino diol and / or a dibasic acid and / or an acid anhydride raw material corresponding to the dibasic acid, a diol monomer containing an amide bond, and a polyester prepolymer;

[0133] Theoretically, when the molar ratio of primary amino diol to dibasic acid and / or its corresponding anhydride is 1:1.01-1:2.00, the polyester prepolymer is a hydroxyl-terminated prepolymer obtained by reacting an excess of diol monomer containing an imide cyclic structure and / or primary amino diol and / or diol monomer containing an imide acyclic structure with the dibasic acid. When the molar ratio of primary amino diol to dibasic acid and / or its corresponding anhydride is 1:2.01-1:6.00, the polyester prepolymer is a carboxyl-terminated prepolymer obtained by reacting an excess of diol monomer containing an imide cyclic structure and / or primary amino diol and / or diol monomer containing an imide acyclic structure with the dibasic acid.

[0134] First, each component of the above composition can participate in the polyester reaction without causing raw material loss. Second, when the sum of the molar proportions of the polyester prepolymer obtained by reacting the diol monomer containing an imide ring structure and the dibasic monomer containing an imide ring structure in the composition exceeds 80%, preferably exceeds 90%, and more preferably exceeds 95%. In other words, if one or more organic impurities in the primary amino diol, diol containing an amide bond, or dibasic acid do not exceed 20%, the performance of the entire polyester is within a controllable range, and the impact on the overall resin structure is minimal and almost negligible.

[0135] It is worth noting that the amino and hydroxyl groups in the primary amino diol act as two independent reactive units. Without affecting their reactivity, they can undergo a cyclization reaction to form an imide and an esterification / transesterification reaction based on their reactivity. The order of the two reactions does not affect the structure of the polymer strength-enhancing segments in the final product. Therefore, those skilled in the art can also perform an esterification / transesterification reaction on the primary amino diol with a dibasic acid / ester to obtain a polyester copolymer containing primary amino groups; and then perform a cyclization reaction on the polyester copolymer containing primary amino groups with a dibasic acid and / or its corresponding anhydride to form an imide to obtain a polyester copolymer containing the polymer strength-enhancing segments shown in Formula (III).

[0136] IV. Polymers containing other modified structural units

[0137] The polymers of the present invention may optionally include heat-resistant, transparent or high-barrier modifying units.

[0138] V. Alloy

[0139] The polymers of the present invention may form alloys with each other or optionally with other polymers.

[0140] VI. Compositions and Molded Articles

[0141] The present invention also provides a composition or a molded body of the above polymer. Methods for processing or molding various types of polymers are known in the art.

[0142] Taking polyester copolymers as an example, the polyester composition of the present invention further comprises a plasticizer, a crystal nucleating agent or a hydrolysis inhibitor in addition to the aforementioned strength-enhancing polymer.

[0143] The polyester composition of the present invention may contain, as other components besides those mentioned above, fillers (inorganic fillers, organic fillers), flame retardants, antioxidants, hydrocarbon waxes or anionic surfactants (i.e., lubricants), ultraviolet absorbers, antistatic agents, anti-corona agents, light stabilizers, pigments, mildewproofing agents, antibacterial agents, foaming agents, etc., within a range that does not impair the effects of the present invention. Similarly, other polymer materials and other resin compositions may be added within a range that does not impair the effects of the present invention.

[0144] The polyester composition of the present invention can be prepared into a molded body such as a sheet by extrusion molding or press molding; the obtained sheet can also be further thermoformed in a temperature range above the glass transition temperature (Tg) and below the melting point (Tm) of the polyester resin composition, for example, stretched into a film.

[0145] VII. Products and Applications

[0146] The polymer, alloy thereof, or composition or molded article of the present invention is suitable for use in food containers, food packaging films, disposable tableware such as spoons or straws, transparent boxes for daily necessities, cosmetics, home appliances, etc., transparent windows for cardboard boxes, etc., transparent folders, ID holders and other stationery, industrial films or agricultural films, and chemical fibers for clothing or industry.

[0147] VIII. Technical Terms

[0148] Structural units and segments

[0149] The structural unit, also known as the monomer unit, is the smallest indivisible structural unit included in the polymer. It has the same structure as the monomer except for the functional group that undergoes polymerization. In a binary copolymer, two different structural units are contained and can be divided into random copolymers, alternating copolymers or block copolymers, etc. The polymer of the present invention is preferably a random copolymer.

[0150] In random copolymers and block copolymers, polymer chains in which the same monomers appear repeatedly are referred to as segments in this application, for example:

[0151] It refers to a polymer chain in which the structural unit is repeated three times.

[0152] Melt flow index

[0153] The melt flow index of the present invention is tested according to ASTM-D1238, with a unit of g / 10 min and an error range of ±5.

[0154] Amino-containing diols

[0155] The amino-containing diol in the present invention has the following structure: OH-R2(NH2)-OH. The amino-containing diol can be selected from an alkanediolamine that is unsubstituted or substituted with a substituent selected from a halogen, alkyl, or nitro group, or an alkyl-aryl-alkanediolamine that is unsubstituted or substituted with a substituent selected from a halogen, alkyl, or nitro group. Preferably, the amino-containing diol can be selected from at least one of 3-amino-1,2-propylene glycol, 2-amino-1,3-propylene glycol, 2-amino-1,3-butanediol, 2-amino-1,4-butanediol, 2-amino-1,5-pentanediol, 3-amino-1,5-pentanediol, 5-amino-1,3-benzenedimethanol, and 2-amino-1,3-phenylenedimethanol.

[0156] Dicarboxylic acids that are easily cyclized OOC-R1-COOH

[0157] The HOOC-R1-COOH is a dicarboxylic acid that readily cyclizes, i.e., a dicarboxylic acid that readily forms a cyclic anhydride in the absence of a catalyst or under catalytic conditions. Dicarboxylic acids that readily cyclize are known to those skilled in the art, for example, see CN110790906B. HOOC-R1-COOH may be selected from an alkanedicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl, an alkanedicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl and is interrupted by one or more O atoms, an alkenedicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen or alkyl, a cycloalkanedicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a cycloalkenedicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, an aromatic dicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, or a bridged cyclic dicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro. Preferably, HOOC-R1-COOH can be selected from at least one of succinic acid, 2-methylsuccinic acid, 2-phenylsuccinic acid, 2-benzylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, 2,3-diphenylsuccinic acid, 1,2-cyclobutanedicarboxylic acid, 2,2,3,3-tetramethylsuccinic acid, methylmaleic acid, dimethylmaleic acid, phthalic acid, hexahydrophthalic acid, norbornenic acid, tetrahydrophthalic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 3-phenylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, diglycolic acid, 2,3-furandicarboxylic acid, 3,4-furandicarboxylic acid, 2,3-pyridinedicarboxylic acid, and 3,4-pyridinedicarboxylic acid. The cyclic anhydride of HOOC-R1-COOH can be preferably selected from succinic anhydride, 2-methylsuccinic anhydride, 2-phenylbutyric anhydride, 2-benzylsuccinic anhydride, 2,2-dimethylsuccinic anhydride, 2,3-dimethylsuccinic anhydride, 2,3-diphenylsuccinic anhydride, 1,2-cyclosuccinic anhydride, 2,2,3,3-tetramethylsuccinic anhydride, methylmaleic anhydride, dimethylmaleic anhydride, phthalic anhydride At least one of dihydrophthalic anhydride, hexahydrophthalic anhydride, nadic anhydride, tetrahydrophthalic anhydride, glutaric anhydride, 2-methylglutaric anhydride, 3-methylglutaric anhydride, 3-phenylglutaric anhydride, 2,2-dimethylglutaric anhydride, 3,3-dimethylglutaric anhydride and diglycolic anhydride, 2,3-furandicarboxylic anhydride, 3,4-furandicarboxylic anhydride, 2,3-pyridinedicarboxylic anhydride and 3,4-pyridinedicarboxylic anhydride.

[0158] Dicarboxylic acids for polymer synthesis

[0159] The dicarboxylic acid used for polymer synthesis in the present invention can be used for the synthesis of polymer bulk structural units, and can also be used for the synthesis of structural units for improving polymer strength. When used for the synthesis of structural units for improving polymer strength, that is, HOOC-R3-COOH defined in the present invention, it can be any dicarboxylic acid different from HOOC-R2-COOH, for example, it can be the easily cyclized dicarboxylic acid described above for HOOC-R2-COOH; or it can be a dicarboxylic acid that is not easily cyclized, such as terephthalic acid, 2,5-furandicarboxylic acid, oxalic acid, malonic acid, 1,6-hexanediol, 1,10-decanedioic acid, and 1,18-octadecanediol. Preferably, HOOC-R3-COOH can be selected from an alkane dicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl, an alkane dicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl and is interrupted by one or more O atoms, an alkene dicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen or alkyl, a cycloalkane dicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a cycloalkene dicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, an aromatic dicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, or a bridged cyclic dicarboxylic acid which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro. Preferably, HOOC-R3-COOH can be selected from succinic acid, 2-methylsuccinic acid, 2-phenylsuccinic acid, 2-benzylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, 2,3-diphenylsuccinic acid, 1,2-cyclobutanediol, 2,2,3,3-tetramethylsuccinic acid, oxalic acid, malonic acid, 1,6-hexanediol, 1,10-decanedioic acid, 1,18-octadecanedioic acid, maleic acid, methylmaleic acid, dioctadecanedioic ... 1,6-hexanediol, 1,10-decanedioic acid, 1,18-octadecanedioic acid, 1,6-hexanediol, 1,10-decanedioic acid, 1,18-octadecanedioic acid, 1,6-hexanediol, 1,6-hexanediol, 1,10-decanedioic acid, 1,18-octadecanedioic acid, 1,6-hexanediol, 1,6-hexanediol, 1,10-decanedioic acid, 1,18-octadecanedioic acid, 1,6-hexanediol, 1,6-hexanediol, 1,6-hexanediol, 1,6-hexanediol, 1,6-hex At least one of methylmaleic acid, phthalic acid, hexahydrophthalic acid, norbornenic acid, tetrahydrophthalic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 3-phenylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, diglycolic acid, 2,3-furandicarboxylic acid, 3,4-furandicarboxylic acid, 2,3-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, terephthalic acid, and 2,5-furandicarboxylic acid.

[0160] Diols for polymer synthesis

[0161] The diol used for polymer synthesis can be selected from alkylene glycols that are unsubstituted or substituted with substituents selected from halogen, alkyl or nitro groups, OH-alkylene-cycloalkylene-alkylene-OH that are unsubstituted or substituted with substituents selected from halogen, alkyl or nitro groups, polyether glycols, or alkylene glycols interrupted by one or more nitrogen atoms; preferably, at least one selected from alkylene glycols containing 2 to 18 carbon atoms, polyethylene glycol, polypropylene glycol, polytetrahydrofuran diol, N-methyldiethanolamine, and N-ethyldiethanolamine. Preferably, at least one selected from ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,18-octadecanediol, polyethylene glycol, and 1,4-cyclohexanedimethanol.

[0162] Polyester structural unit

[0163] The polyester structural unit used in the present invention has the common meaning in the art, and is preferably formed by polycondensation of the above-mentioned dicarboxylic acid used for polymer synthesis and diol used for polymer synthesis.

[0164] Organic Definition

[0165] When a numerical range is listed, it is intended to include every value and sub-range within the stated range. For example, "C 1-6 "Alkyl" includes C1, C2, C3, C4, C5, C6, C 1-6 、C 1-5 、C 1-4 、C 1-3 、C 1-2 、C 2-6 、C 2-5 、C 2-4 、C 2-3 、C 3-6 、C 3-5 、C 3-4 、C 4-6 、C 4-5 and C 5-6 alkyl.

[0166] In the present invention, alkyl refers to a chain or branched saturated hydrocarbon group with a corresponding number of carbon atoms, such as "C 1-6 "Alkyl" refers to a straight or branched chain saturated hydrocarbon group having 1 to 6 carbon atoms. In some embodiments, C 1-4 Alkyl and C 1-2 Alkyl groups are preferred. 1-6Examples of alkyl groups include: methyl (C1), ethyl (C2), n-propyl (C3), isopropyl (C3), n-butyl (C4), tert-butyl (C4), sec-butyl (C4), isobutyl (C4), n-pentyl (C5), 3-pentyl (C5), pentyl (C5), neopentyl (C5), 3-methyl-2-butyl (C5), tert-pentyl (C5), and n-hexyl (C6). The term “C 1-6 "Alkyl" also includes heteroalkyl groups in which one or more (e.g., 1, 2, 3, or 4) carbon atoms are replaced by heteroatoms (e.g., oxygen, sulfur, nitrogen, boron, silicon, phosphorus). The alkyl group may be optionally substituted with one or more substituents, for example, 1 to 5 substituents, 1 to 3 substituents, or 1 substituent. Conventional alkyl abbreviations include: Me (-CH3), Et (-CH2CH3), iPr (-CH(CH3)2), nPr (-CH2CH2CH3), n-Bu (-CH2CH2CH2CH3), or i-Bu (-CH2CH(CH3)2). In other embodiments, "C 6-24 "Alkyl" is preferred, such as C6, C7, C8, C9, C 10 , C 11 , C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , C 18 , C 19 , C 20 , C 21 , C 22 , C 23 , C 24 , and preferably a straight-chain alkyl group.

[0167] In the present invention, "alkenyl" refers to a straight-chain or branched hydrocarbon group having corresponding carbon atoms and at least one carbon-carbon double bond, such as "C 2-6 "Alkenyl" refers to a straight or branched chain hydrocarbon group having 2 to 6 carbon atoms and at least one carbon-carbon double bond. In some embodiments, C 2-4 Alkenyl is preferred. 2-6 Examples of alkenyl groups include ethenyl (C2), 1-propenyl (C3), 2-propenyl (C3), 1-butenyl (C4), 2-butenyl (C4), butadienyl (C4), pentenyl (C5), pentadienyl (C5), hexenyl (C6), and the like. The term "C 2-6"Alkenyl" also includes heteroalkenyl groups in which one or more (e.g., 1, 2, 3, or 4) carbon atoms are replaced by heteroatoms (e.g., oxygen, sulfur, nitrogen, boron, silicon, phosphorus). The alkenyl group may be optionally substituted with one or more substituents, for example, 1 to 5 substituents, 1 to 3 substituents, or 1 substituent. In other embodiments, "C 6-24 Alkenyl" is preferred, such as C6, C7, C8, C9, C 10 , C 11 , C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , C 18 , C 19 , C 20 , C 21 , C 22 , C 23 , C 24 , and preferably a straight chain alkenyl group, preferably containing multiple olefinic bonds.

[0168] “C 2-6 "Alkynyl" refers to a straight or branched chain hydrocarbon group having 2 to 6 carbon atoms, at least one carbon-carbon triple bond, and optionally one or more carbon-carbon double bonds. In some embodiments, C 2-4 Alkynyl is preferred. 2-6 Examples of alkynyl groups include, but are not limited to, ethynyl (C2), 1-propynyl (C3), 2-propynyl (C3), 1-butynyl (C4), 2-butynyl (C4), pentynyl (C5), hexynyl (C6), and the like. The term "C 2-6 "Alkynyl" also includes heteroalkynyl groups, in which one or more (e.g., 1, 2, 3, or 4) carbon atoms are replaced by heteroatoms (e.g., oxygen, sulfur, nitrogen, boron, silicon, phosphorus). Alkynyl groups can be optionally substituted with one or more substituents, for example, 1 to 5 substituents, 1 to 3 substituents, or 1 substituent. In other embodiments, "C 6-24 Alkenyl" is preferred, such as C6, C7, C8, C9, C 10 , C 11 , C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , C 18 , C 19 , C 20 , C 21 , C 22 , C 23 , C 24 , and preferably a straight-chain alkynyl group.

[0169] “C 1-10 "Alkylene" refers to the removal of C 1-10 In some embodiments, C 1-4 Alkylene, C 2-4 Alkylene and C 1-3 Alkylene is preferred. Unsubstituted alkylene includes, but is not limited to, methylene (-CH2-), ethylene (-CH2CH2-), propylene (-CH2CH2CH2-), butylene (-CH2CH2CH2CH2-), pentylene (-CH2CH2CH2CH2CH2-), hexylene (-CH2CH2CH2CH2CH2CH2-), and the like. Exemplary substituted alkylenes, for example, alkylenes substituted with one or more alkyl (methyl) groups, include, but are not limited to, substituted methylene (-CH(CH3)-, -C(CH3)2-), substituted ethylene (-CH(CH3)CH2-, -CH2CH(CH3)-, -C(CH3)2CH2-, -CH2C(CH3) 2- ), substituted propylene (-CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-, -CH2CH2CH(CH3)-, -C(CH3)2CH2CH2-, -CH2C(CH3)2CH2-, -CH2CH2C(CH3)2-), and the like.

[0170] “C 2-10 "Alkenylene" refers to the removal of C 2-10 In some embodiments, C 2-4 Alkenylene is particularly preferred. Exemplary unsubstituted alkenylene groups include, but are not limited to, vinylene (-CH=CH-) and propenylene (e.g., -CH=CHCH2-, -CH2-CH=CH-). Exemplary substituted alkenylene groups, for example, alkenylene groups substituted with one or more alkyl (methyl) groups, include, but are not limited to, substituted ethylene (-C(CH3)=CH-, -CH=C(CH3)-), substituted propenylene (-C(CH3)=CHCH2-, -CH=C(CH3)CH2-, -CH=CHCH(CH3)-, -CH=CHC(CH3)2-, -CH(CH3)-CH=CH-, -C(CH3)2-CH=CH-, -CH2-C(CH3)=CH-, -CH2-CH=C(CH3)-), and the like.

[0171] “C 2-10 "Alkynylidene" refers to the removal of C 2-10In some embodiments, C 2-4 Alkyne is particularly preferred. Exemplary alkynyl includes, but is not limited to, ethynyl (-C≡C-), substituted or unsubstituted propynyl (-C≡CCH2-), and the like.

[0172] “C 0-6 "Alkylene" refers to the chemical bond and the above-mentioned "C 1-6 Alkylene", "C 0-4 "Alkylene" refers to the chemical bond and the above-mentioned "C 1-4 "Alkylene".

[0173] "Halo" or "halogen" refers to fluorine (F), chlorine (Cl), bromine (Br) and iodine (I).

[0174] Therefore, “C 1-6 "Haloalkyl" refers to the above-mentioned "C 1-6 Alkyl", which is substituted by one or more halogen groups. In some embodiments, C 1-4 Halogenated alkyl is particularly preferred, more preferably C 1-2 Haloalkyl. Exemplary haloalkyl groups include, but are not limited to, -CF3, -CH2F, -CHF2, -CHFCH2F, -CH2CHF2, -CF2CF3, -CCl3, -CH2Cl, -CHCl2, 2,2,2-trifluoro-1,1-dimethyl-ethyl, and the like. The haloalkyl group can be substituted at any available point of attachment, for example, with 1 to 5 substituents, 1 to 3 substituents, or 1 substituent.

[0175] “C 3-10 "Cycloalkyl" refers to a non-aromatic cyclic hydrocarbon group having 3 to 10 ring carbon atoms and zero heteroatoms, optionally containing 1, 2 or 3 double or triple bonds. In some embodiments, C 5-10 Cycloalkyl, C 3-7 Cycloalkyl and C 3-6 Cycloalkyl is particularly preferred, more preferably C 5-7 Cycloalkyl and C 5-6Cycloalkyl. Cycloalkyl also includes ring systems in which the above-mentioned cycloalkyl ring is fused to one or more aryl or heteroaryl groups, wherein the point of attachment is on the cycloalkyl ring, and in such cases, the number of carbons continues to represent the number of carbons in the cycloalkyl system. Cycloalkyl also includes cycloalkyl rings in which the substituents on any non-adjacent carbon atoms are linked to form a bridged ring, together forming a polycycloalkane sharing two or more carbon atoms. Cycloalkyl also includes cycloalkyl rings in which the substituents on the same carbon atom are linked to form a ring, together forming a polycycloalkane sharing one carbon atom. Exemplary cycloalkyl groups include, but are not limited to, cyclopropyl (C3), cyclopropenyl (C3), cyclobutyl (C4), cyclobutenyl (C4), cyclopentyl (C5), cyclopentenyl (C5), cyclohexyl (C6), cyclohexenyl (C6), cyclohexadienyl (C6), cycloheptyl (C7), cycloheptenyl (C7), cycloheptadienyl (C7), cycloheptatrienyl (C7), and the like. A cycloalkyl group can be optionally substituted with one or more substituents, for example, with 1 to 5 substituents, 1 to 3 substituents, or 1 substituent.

[0176] “C 3-10 "Cycloalkylene" refers to the removal of C 3-10 In some embodiments, C 3-6 Cycloalkylene and C 3-4 Cycloalkylene is particularly preferred, and cyclopropylene is especially preferred.

[0177] "3-10 membered heterocyclyl" refers to a saturated or unsaturated radical of a 3- to 10-membered non-aromatic ring system having ring carbon atoms and 1 to 5 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen, sulfur, boron, phosphorus, and silicon, and optionally containing 1, 2, or 3 double or triple bonds. In heterocyclyl groups containing one or more nitrogen atoms, the point of attachment may be a carbon or nitrogen atom, as valence permits. In some embodiments, a 5-10 membered heterocyclyl is preferred, which is a 5-10 membered non-aromatic ring system having ring carbon atoms and 1 to 5 ring heteroatoms; in some embodiments, a 3-7 membered heterocyclyl is preferred, which is a 3-7 membered non-aromatic ring system having ring carbon atoms and 1 to 4 ring heteroatoms; a 5-7 membered heterocyclyl is preferred, which is a 5-7 membered non-aromatic ring system having ring carbon atoms and 1 to 3 ring heteroatoms; a 3-6 membered heterocyclyl is preferred, which is a 3-6 membered non-aromatic ring system having ring carbon atoms and 1 to 3 ring heteroatoms; a 4-6 membered heterocyclyl is preferred, which is a 4-6 membered non-aromatic ring system having ring carbon atoms and 1 to 3 ring heteroatoms; and a 5-6 membered heterocyclyl is more preferred, which is a 5-6 membered non-aromatic ring system having ring carbon atoms and 1 to 3 ring heteroatoms. Heterocyclyl also includes a ring system in which the above-mentioned heterocyclyl ring is fused to one or more cycloalkyl groups, wherein the point of attachment is on the heterocyclyl ring, or a ring system in which the above-mentioned heterocyclyl ring is fused to one or more aryl or heteroaryl groups, wherein the point of attachment is on the heterocyclyl ring; and in such a case, the number of ring members continues to represent the number of ring members in the heterocyclyl ring system. Heterocyclyl also includes a heterocyclyl ring in which any substituents on non-adjacent carbon or nitrogen atoms are connected to form a bridged ring, together forming a polycyclic heteroalkane sharing two or more carbon or nitrogen atoms. Heterocyclyl also includes a heterocyclyl ring in which the substituents on the same carbon atom are connected to form a ring, together forming a polycyclic heteroalkane sharing one carbon atom. Exemplary 3-membered heterocyclyls containing one heteroatom include, but are not limited to, aziridine, oxirane, and thiorenyl. Exemplary 4-membered heterocyclyls containing one heteroatom include, but are not limited to, azetidinyl, oxirane, and thiidine. Exemplary 5-membered heterocyclic groups containing one heteroatom include, but are not limited to, tetrahydrofuranyl, dihydrofuranyl, tetrahydrothiophenyl, dihydrothiophenyl, pyrrolidinyl, dihydropyrrolyl, and pyrrolyl-2,5-dione. Exemplary 5-membered heterocyclic groups containing two heteroatoms include, but are not limited to, pyrazolidinyl, dioxolanyl, oxasulfuranyl, disulfuranyl, and oxazolidin-2-one. Exemplary 5-membered heterocyclic groups containing three heteroatoms include, but are not limited to, triazolinyl, oxadiazolinyl, and thiadiazolinyl. Exemplary 6-membered heterocyclic groups containing one heteroatom include, but are not limited to, piperidinyl, tetrahydropyranyl, dihydropyridinyl, and thianyl.Exemplary 6-membered heterocyclyls containing two heteroatoms include, but are not limited to, piperazinyl, morpholinyl, dithianyl, and dioxanyl. Exemplary 6-membered heterocyclyls containing three heteroatoms include, but are not limited to, hexahydrotriazinyl (triazinanyl). Exemplary 7-membered heterocyclyls containing one heteroatom include, but are not limited to, azepanyl, oxepanyl, and thiepanyl. Exemplary 5-membered heterocyclyls fused to a C6 aryl ring (also referred to herein as 5,6-bicyclic heterocyclyls) include, but are not limited to, dihydroindolinyl, isoindolinyl, dihydrobenzofuranyl, dihydrobenzothienyl, benzoxazolinone, and the like. Exemplary 6-membered heterocyclyls fused to a C6 aryl ring (also referred to herein as 6,6-bicyclic heterocyclyls) include, but are not limited to, tetrahydroquinolinyl, tetrahydroisoquinolinyl, and the like. Heterocyclyl also includes the above-mentioned heterocyclyl and a cycloalkyl, heterocyclyl, aryl or heteroaryl group sharing one or two atoms to form a bridged ring or spirocycle. As long as the valence permits, the shared atom can be a carbon or nitrogen atom. Heterocyclyl also includes the above-mentioned heterocyclyl and heterocyclyl groups that may be optionally substituted with one or more substituents, for example, 1 to 5 substituents, 1 to 3 substituents or 1 substituent.

[0178] “C 6-10 "Aryl" refers to a monocyclic or polycyclic (e.g., bicyclic) 4n+2 aromatic ring system (e.g., having 6 or 10 π electrons shared in a cyclic arrangement) having 6-10 ring carbon atoms and zero heteroatoms. In some embodiments, an aryl group has six ring carbon atoms ("C6 aryl"; e.g., phenyl). In some embodiments, an aryl group has ten ring carbon atoms ("C 10 Aryl also includes ring systems in which an aryl ring as described above is fused to one or more cycloalkyl or heterocyclyl groups, and the point of attachment is on the aryl ring, in which case the number of carbon atoms continues to refer to the number of carbon atoms in the aryl ring system. Aryl groups can be optionally substituted with one or more substituents, for example, with 1 to 5 substituents, 1 to 3 substituents, or 1 substituent.

[0179] "5-14 membered heteroaryl" refers to a group of a 5-14 membered monocyclic or bicyclic 4n+2 aromatic ring system (e.g., having 6, 10, or 14 π electrons shared in a cyclic arrangement) having ring carbon atoms and 1-4 ring heteroatoms, wherein each heteroatom is independently selected from nitrogen, oxygen, and sulfur. In heteroaryl groups containing one or more nitrogen atoms, the point of attachment may be a carbon or nitrogen atom as long as valence permits. Heteroaryl bicyclic ring systems may include one or more heteroatoms in one or both rings. Heteroaryl also includes ring systems in which the above-mentioned heteroaryl rings are fused to one or more cycloalkyl or heterocyclyl groups, and the point of attachment is on the heteroaryl ring, in which case the number of carbon atoms continues to represent the number of carbon atoms in the heteroaryl ring system. In some embodiments, 5-10 membered heteroaryl is preferred, which is a 5-10 membered monocyclic or bicyclic 4n+2 aromatic ring system having ring carbon atoms and 1-4 ring heteroatoms. In other embodiments, 5-6 membered heteroaryls are particularly preferred and are 5-6 membered monocyclic or bicyclic 4n+2 aromatic ring systems having ring carbon atoms and 1-4 ring heteroatoms. Exemplary 5-membered heteroaryls containing one heteroatom include, but are not limited to, pyrrolyl, furanyl, and thienyl. Exemplary 5-membered heteroaryls containing two heteroatoms include, but are not limited to, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, and isothiazolyl. Exemplary 5-membered heteroaryls containing three heteroatoms include, but are not limited to, triazolyl, oxadiazolyl (e.g., 1,2,4-oxadiazolyl), and thiadiazolyl. Exemplary 5-membered heteroaryls containing four heteroatoms include, but are not limited to, tetrazolyl. Exemplary 6-membered heteroaryls containing one heteroatom include, but are not limited to, pyridinyl or pyridonyl. Exemplary 6-membered heteroaryls containing two heteroatoms include, but are not limited to, pyridazinyl, pyrimidinyl, and pyrazinyl. Exemplary 6-membered heteroaryl groups containing three or four heteroatoms include, but are not limited to, triazinyl and tetrazinyl, respectively. Exemplary 7-membered heteroaryl groups containing one heteroatom include, but are not limited to, azacycloheptatrienyl, oxepinyl, and thieptatrienyl. Exemplary 5,6-bicyclic heteroaryl groups include, but are not limited to, indolyl, isoindolyl, indazolyl, benzotriazolyl, benzothiophenyl, isobenzothiophenyl, benzofuranyl, benzisofuranyl, benzimidazolyl, benzoxazolyl, benzisoxazolyl, benzoxadiazolyl, benzothiazolyl, benzisothiazolyl, benzothiadiazolyl, indanyl, and purinyl. Exemplary 6,6-bicyclic heteroaryl groups include, but are not limited to, naphthyridinyl, pteridinyl, quinolinyl, isoquinolinyl, cinnolinyl, quinoxalinyl, phthalazinyl, and quinazolinyl. A heteroaryl group can be optionally substituted with one or more substituents, for example, with 1 to 5 substituents, 1 to 3 substituents, or 1 substituent.

[0180] "Hydroxyalkyl" refers to an alkyl group substituted with one or more hydroxy groups.

[0181] "Alkoxy" refers to the oxygen ether form of a straight or branched chain alkyl group, i.e., -O-alkyl. Similarly, "methoxy" refers to -O-CH3.

[0182] "Optionally substituted by..." means that it may be substituted by a specified substituent or may be unsubstituted;

[0183] The divalent groups formed by removing another hydrogen from the above-defined alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl and heteroaryl groups are collectively referred to as "subunits". The ring-forming groups such as cycloalkyl, heterocyclyl, aryl and heteroaryl groups are collectively referred to as "cyclyls".

[0184] Alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, and the like are defined herein as optionally substituted groups.

[0185] Exemplary substituents on carbon atoms include, but are not limited to, halogen, -CN, -NO2, -N3, -SO2H, -SO3H, -OH, -OR aa 、-ON(R bb )2、-N(R bb )2、-N(R bb )3 + X - 、-N(OR cc )R bb 、-SH、-SR aa 、-SSR cc 、-C(=O)R aa 、-CO2H、-CHO、-C(OR cc )2, -CO2R aa 、-OC(=O)R aa 、-OCO2R aa 、-C(=O)N(R bb )2、-OC(=O)N(R bb )2、-NR bb C(=O)R aa 、-NR bb CO2R aa 、-NR bb C(=O)N(R bb )2、-C(=NR bb )R aa 、-C(=NR bb )OR aa 、-OC(=NR bb )R aa 、-OC(=NR bb )OR aa 、-C(=NR bb )N(R bb )2、-OC(=NRbb )N(R bb )2、-NR bb C(=NR bb )N(R bb )2、-C(=O)NR bb SO2R aa 、-NR bb SO2R aa 、-SO2N(R bb )2、-SO2R aa 、-SO2OR aa 、-OSO2R aa 、-S(=O)R aa 、-OS(=O)R aa 、-Si(R aa )3、-OSi(R aa )3、-C(=S)N(R bb )2、-C(=O)SR aa 、-C(=S)SR aa 、-SC(=S)SR aa 、-SC(=O)SR aa 、-OC(=O)SR aa 、-SC(=O)OR aa 、-SC(=O)R aa 、-P(=O)2R aa 、-OP(=O)2R aa 、-P(=O)(R aa )2、-OP(=O)(R aa )2、-OP(=O)(OR cc )2、-P(=O)2N(R bb )2、-OP(=O)2N(R bb )2、-P(=O)(NR bb )2、-OP(=O)(NR bb )2、-NR bb P(=O)(OR cc )2、-NR bb P(=O)(NR bb )2、-P(R cc )2、-P(R cc )3、-OP(R cc )2、-OP(R cc )3、-B(R aa )2、-B(OR cc )2、-BR aa (OR cc), alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl and heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl and heteroaryl is independently replaced by 0, 1, 2, 3, 4 or 5 R dd group substitution;

[0186] Or the two geminal hydrogen atoms on the carbon atom are replaced by groups =O, =S, =NN(R bb )2, =NNR bb C(=O)R aa 、=NNR bb C(=O)OR aa 、=NNR bb S(=O)2R aa 、=NR bb or = NOR cc replace;

[0187] R aa Each of R is independently selected from alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl and heteroaryl, or two R aa The groups are combined to form a heterocyclyl or heteroaryl ring, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl and heteroaryl group is independently replaced by 0, 1, 2, 3, 4 or 5 R dd group substitution;

[0188] R bb Each of the following is independently selected from: hydrogen, -OH, -OR aa 、-N(R cc )2, -CN, -C(=O)R aa 、-C(=O)N(R cc )2, -CO2R aa 、-SO2R aa 、-C(=NR cc )OR aa 、-C(=NR cc )N(R cc )2、-SO2N(R cc )2, -SO2R cc 、-SO2OR cc 、-SOR aa 、-C(=S)N(R cc )2, -C(=O)SR cc 、-C(=S)SR cc 、-P(=O)2R aa 、-P(=O)(R aa )2、-P(=O)2N(R cc )2、-P(=O)(NR cc)2, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl and heteroaryl, or two R bb The groups are combined to form a heterocyclyl or heteroaryl ring, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl and heteroaryl group is independently replaced by 0, 1, 2, 3, 4 or 5 R dd group substitution;

[0189] R cc Each of R is independently selected from hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl and heteroaryl, or two R cc The groups are combined to form a heterocyclyl or heteroaryl ring, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl and heteroaryl group is independently replaced by 0, 1, 2, 3, 4 or 5 R dd group substitution;

[0190] R dd Each of the is independently selected from: halogen, -CN, -NO2, -N3, -SO2H, -SO3H, -OH, -OR ee 、-ON(R ff )2、-N(R ff )2,、-N(R ff )3 + X - 、-N(OR ee )R ff 、-SH、-SR ee 、-SSR ee 、-C(=O)R ee 、-CO2H、-CO2R ee 、-OC(=O)R ee 、-OCO2R ee 、-C(=O)N(R ff )2、-OC(=O)N(R ff )2、-NR ff C(=O)R ee 、-NR ff CO2R ee 、-NR ff C(=O)N(R ff )2、-C(=NR ff )OR ee 、-OC(=NR ff )R ee 、-OC(=NR ff )OR ee 、-C(=NR ff )N(R ff )2、-OC(=NR ff )N(R ff)2、-NR ff C(=NR ff )N(R ff )2、-NR ff SO2R ee 、-SO2N(R ff )2, -SO2R ee 、-SO2OR ee 、-OSO2R ee 、-S(=O)R ee 、-Si(R ee )3、-OSi(R ee )3、-C(=S)N(R ff )2, -C(=O)SR ee 、-C(=S)SR ee 、-SC(=S)SR ee 、-P(=O)2R ee 、-P(=O)(R ee )2、-OP(=O)(R ee )2、-OP(=O)(OR ee )2, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl, heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl and heteroaryl is independently substituted by 0, 1, 2, 3, 4 or 5 R gg Group substitution, or two geminal R dd Substituents may combine to form =O or =S;

[0191] R ee Each of R is independently selected from alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl and heteroaryl, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl and heteroaryl is independently replaced by 0, 1, 2, 3, 4 or 5 R gg group substitution;

[0192] R ff Each of R is independently selected from hydrogen, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl and heteroaryl, or two R ff The groups are combined to form a heterocyclic or heteroaryl ring, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclic, aryl and heteroaryl group is independently replaced by 0, 1, 2, 3, 4 or 5 R gg group substitution;

[0193] R gg Each of the independently: halogen, -CN, -NO2, -N3, -SO2H, -SO3H, -OH, -OC 1-6 Alkyl, -ON(C 1-6 Alkyl)2, -N(C1-6 Alkyl)2, -N(C 1-6 Alkyl)3 + X - 、-NH(C 1-6 Alkyl)2 + X - 、-NH2(C 1-6 alkyl) + X - 、-NH3 + X - 、-N(OC 1-6 Alkyl)(C 1-6 Alkyl), -N(OH)(C 1-6 Alkyl), -NH(OH), -SH, -SC 1-6 Alkyl, -SS(C 1-6 alkyl), -C(=O)(C 1-6 alkyl), -CO2H, -CO2(C 1-6 alkyl), -OC(=O)(C 1-6 Alkyl), -OCO2(C 1-6 alkyl), -C(=O)NH2, -C(=O)N(C 1-6 alkyl)2, -OC(=O)NH(C 1-6 alkyl), -NHC(=O)(C 1-6 Alkyl), -N(C 1-6 alkyl)C(=O)(C 1-6 Alkyl), -NHCO2(C 1-6 alkyl), -NHC(=O)N(C 1-6 Alkyl)2, -NHC(=O)NH(C 1-6 alkyl), -NHC(=O)NH2, -C(=NH)O(C 1-6 alkyl), -OC(=NH)(C 1-6 alkyl), -OC(=NH)OC 1-6 Alkyl, -C(=NH)N(C 1-6 Alkyl)2, -C(=NH)NH(C 1-6 alkyl), -C(=NH)NH2, -OC(=NH)N(C 1-6 Alkyl)2, -OC(NH)NH(C 1-6 alkyl), -OC(NH)NH2, -NHC(NH)N(C 1-6 Alkyl)2, -NHC(=NH)NH2, -NHSO2(C 1-6 Alkyl), -SO2N(C 1-6 Alkyl)2, -SO2NH(C 1-6 alkyl), -SO2NH2, -SO2C1-6 Alkyl, -SO2OC 1-6 Alkyl, -OSO2C 1-6 Alkyl, -SOC 1-6 Alkyl, -Si(C 1-6 alkyl)3, -OSi(C 1-6 alkyl)3, -C(=S)N(C 1-6 alkyl)2、C(=S)NH(C 1-6 alkyl), C(=S)NH2, -C(=O)S(C 1-6 alkyl), -C(=S)SC 1-6 Alkyl, -SC(=S)SC 1-6 Alkyl, -P(=O)2(C 1-6 alkyl), -P(=O)(C 1-6 alkyl)2, -OP(=O)(C 1-6 alkyl)2, -OP(=O)(OC 1-6 Alkyl)2, C 1-6 Alkyl, C 1-6 Halogenated alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C7 cycloalkyl, C6-C 10 Aryl, C3-C7 heterocyclic, C5-C 10 heteroaryl; or two geminal R gg Substituents may combine to form =O or =S; wherein X - For the counter ion.

[0194] Exemplary substituents on nitrogen atoms include, but are not limited to, hydrogen, -OH, -OR aa 、-N(R cc )2, -CN, -C(=O)R aa 、-C(=O)N(R cc )2, -CO2R aa 、-SO2R aa 、-C(=NR bb )R aa 、-C(=NR cc )OR aa 、-C(=NR cc )N(R cc )2、-SO2N(R cc )2, -SO2R cc 、-SO2OR cc 、-SOR aa 、-C(=S)N(R cc )2, -C(=O)SR cc 、-C(=S)SR cc 、-P(=O)2R aa 、-P(=O)(Raa )2、-P(=O)2N(R cc )2、-P(=O)(NR cc )2, alkyl, haloalkyl, alkenyl, alkynyl, cycloalkyl, heterocyclyl, aryl and heteroaryl, or two R attached to the nitrogen atom cc The groups are combined to form a heterocyclic or heteroaryl ring, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, heterocyclic, aryl and heteroaryl group is independently replaced by 0, 1, 2, 3, 4 or 5 R dd Group substituted, and wherein R aa 、R bb 、R cc and R dd As mentioned above.

[0195] The present invention will be further described below with reference to the embodiments. The examples of the embodiments are intended to explain the present invention but should not be construed as limiting the present invention.

[0196] Example 1

[0197] In this embodiment, a diol monomer having a cyclic imide structure is synthesized, and an imide diol-modified PBS is prepared based on the diol monomer.

[0198] 1. Synthesis of diols containing cyclic imide structures

[0199] 911.1 g (10 mol) of 2-amino-1,3-propanediol and 1040.6 g (10 mol) of 1,3-propanedioic acid after vacuum drying were put into a reactor, and 100 ppm each of triphenyl phosphite (thermal stabilizer) and tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentyl erythritol ester (antioxidant) were added (compared to the weight of the entire reaction system, the same below) and stirred at room temperature. At the same time, nitrogen was used to fully replace the air in the reactor. Then, the temperature was slowly raised to 120° C. in a nitrogen atmosphere, the nitrogen flow rate was 150 mL / min, and the mixture was stirred at a constant temperature for 3 hours to obtain a diol composition.

[0200] The diol composition was separated using a liquid chromatography apparatus to obtain a diol having a cyclic imide structure, the structural formula of which is shown in the following formula II-a-1. The conversion rate of the above reaction was calculated to be 45.6%.

[0201] 2. Preparation of cyclic imide diol modified PBS resin material

[0202] 31.83 g (0.2 mol) of the separated diol with a cyclic imide structure, 236 g (2 mol) of succinic acid, and 90 g (1.0 mol) of 1,4-butanediol were weighed and put into a reactor, stirred and heated to melt in nitrogen, 100 ppm of zinc acetate was added when the temperature reached 170°C, and the temperature was kept to react for 3 hours under a negative pressure of -0.03 MPa; then the pressure was restored to normal, 90 g (1.0 mol) of 1,4-butanediol was added, 500 ppm of n-butyl titanate was added, and the temperature was raised to 230°C; the vacuum was slowly evacuated to 1-2 Torr, and vacuum polycondensation was carried out for 9.5 hours to obtain a cyclic imide diol-modified PBS resin material with a melt flow index of 20±5 g / 10 min.

[0203] Example 2

[0204] In this embodiment, a diol monomer having a cyclic imide structure is synthesized, and an imide diol-modified PBS is prepared based on the diol monomer.

[0205] 1. Synthesis of diols containing cyclic imide structures

[0206] 911.1 g (10 mol) of 2-amino-1,3-propanediol and 1180.1 g (10 mol) of 1,4-butanedioic acid after vacuum drying were put into a reactor, and 100 ppm each of triphenyl phosphite (thermal stabilizer) and tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentyl erythritol ester (antioxidant) were added (compared to the weight of the entire reaction system, the same below) and stirred at room temperature. At the same time, nitrogen was used to fully replace the air in the reactor. Then, the temperature was slowly raised to 120° C. in a nitrogen atmosphere, the nitrogen flow rate was 150 mL / min, and the mixture was stirred at a constant temperature for 3 hours to obtain a diol composition.

[0207] The diol composition was separated by liquid chromatography to obtain a diol having a cyclic imide structure, the structural formula of which is shown in the following formula II-b-1. The conversion rate of the above reaction was calculated to be 98.5%.

[0208] In addition, the isolated cyclic imide diol was subjected to H NMR and FTIR spectrometry, and the results are shown in Figures 1 and 2. In the H NMR spectrum (solvent: deuterated dimethyl sulfoxide), there is no H absorption peak of -NH between the chemical shifts of 7.5 and 8.5; in the FTIR spectrum (hot-melt film preparation), there is a peak at 1690 cm - There is a strong absorption peak near 1400cm - 、1180cm - and 822cm - There is a medium-strong peak, 3310-3350cm - and 1500-1530cm- No absorption peak appears, proving that the diol shown in the above formula II-b-1 has been synthesized.

[0209] 2. Preparation of cyclic imide diol modified PBS resin material

[0210] 34.62 g (0.2 mol) of the separated diol with a cyclic imide structure, 236 g (2 mol) of succinic acid, and 90 g (1.0 mol) of 1,4-butanediol were weighed and put into a reactor, stirred and heated to melt in nitrogen, 100 ppm of zinc acetate was added when the temperature reached 170°C, and the temperature was maintained at a negative pressure of -0.03 MPa for 3 hours; then the pressure was restored to normal, 90 g (1.0 mol) of 1,4-butanediol was added, 500 ppm of n-butyl titanate was added, and the temperature was raised to 230°C; the vacuum was slowly evacuated to 1-2 Torr, and vacuum polycondensation was performed for 6.5 hours to obtain a cyclic imide diol-modified PBS resin material with a melt flow index of 20±5 g / 10 min.

[0211] Example 3

[0212] In this embodiment, a diol monomer having a cyclic imide structure is synthesized, and an imide diol-modified PBS is prepared based on the diol monomer.

[0213] 1. Synthesis of diols containing cyclic imide structures

[0214] 911.1 g (10 mol) of 2-amino-1,3-propanediol and 1321.4 g (10 mol) of 1,5-pentanedioic acid after vacuum drying were put into a reactor, and 100 ppm each of triphenyl phosphite (thermal stabilizer) and tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentyl erythritol ester (antioxidant) were added (compared to the weight of the entire reaction system, the same below) and stirred at room temperature. At the same time, nitrogen was used to fully replace the air in the reactor. Then, the temperature was slowly raised to 120° C. in a nitrogen atmosphere, the nitrogen flow rate was 150 mL / min, and the mixture was stirred at a constant temperature for 6 hours to obtain a diol composition.

[0215] The diol composition was separated using a liquid chromatography apparatus to obtain a diol having a cyclic imide structure, the structural formula of which is shown in Formula II-c-1 (see Figure 3 for the NMR spectrum), and the conversion rate of the reaction was calculated to be 95.2%.

[0216] 2. Preparation of cyclic imide diol modified PBS resin material

[0217] 37.42 g (0.2 mol) of the separated diol with a cyclic imide structure, 236 g (2 mol) of succinic acid, and 90 g (1.0 mol) of 1,4-butanediol were weighed and put into a reactor, stirred and heated to melt in nitrogen, 100 ppm of zinc acetate was added when the temperature reached 170°C, and the temperature was maintained at a negative pressure of -0.03 MPa for 3 hours; then the pressure was restored to normal, 90 g (1.0 mol) of 1,4-butanediol was added, 500 ppm of n-butyl titanate was added, and the temperature was raised to 230°C; the vacuum was slowly evacuated to 1-2 Torr, and vacuum polycondensation was carried out for 8.0 hours to obtain a cyclic imide diol-modified PBS resin material with a melt flow index of 20±5 g / 10 min.

[0218] Example 4

[0219] In this embodiment, a diol monomer having a cyclic imide structure is synthesized, and an imide diol-modified PBS is prepared based on the diol monomer.

[0220] 1. Synthesis of diols containing cyclic imide structures

[0221] 911.1 g (10 mol) of 2-amino-1,3-propanediol and 1461.4 g (10 mol) of 1,6-hexanediol after vacuum drying were put into a reactor, and 100 ppm each of triphenyl phosphite (thermal stabilizer) and tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentyl erythritol ester (antioxidant) were added (compared to the weight of the entire reaction system, the same below) and stirred at room temperature. At the same time, nitrogen was used to fully replace the air in the reactor. Then, the temperature was slowly raised to 120° C. in a nitrogen atmosphere, the nitrogen flow rate was 150 mL / min, and the mixture was stirred at a constant temperature for 6 hours to obtain a diol composition.

[0222] The diol composition was separated using a liquid chromatography apparatus to obtain a diol having a cyclic imide structure, the structural formula of which is shown in the following formula II-d-1. The conversion rate of the above reaction was calculated to be 62.1%.

[0223] 2. Preparation of cyclic imide diol modified PBS resin material

[0224] 40.22 g (0.2 mol) of the separated diol with a cyclic imide structure, 236 g (2 mol) of succinic acid, and 90 g (1.0 mol) of 1,4-butanediol were weighed and put into a reactor, stirred and heated to melt in nitrogen, 100 ppm of zinc acetate was added when the temperature reached 170°C, and the temperature was maintained at a negative pressure of -0.03 MPa for 3 hours; then the pressure was restored to normal, 90 g (1.0 mol) of 1,4-butanediol was added, 500 ppm of n-butyl titanate was added, and the temperature was raised to 230°C; the vacuum was slowly evacuated to 1-2 Torr, and vacuum polycondensation was performed for 10.5 hours to obtain a cyclic imide diol-modified PBS resin material with a melt flow index of 20±5 g / 10 min.

[0225] Example 5

[0226] In this embodiment, a diol monomer having a cyclic imide structure is synthesized, and an imide diol-modified PBS is prepared based on the diol monomer.

[0227] 1. Synthesis of diols containing cyclic imide structures

[0228] 911.1 g (10 mol) of 3-amino-1,2-propanediol and 1180.1 g (10 mol) of 1,4-butanedioic acid after vacuum drying were put into a reactor, and 100 ppm each of triphenyl phosphite (thermal stabilizer) and tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentyl erythritol ester (antioxidant) were added (compared to the weight of the entire reaction system, the same below) and stirred at room temperature. At the same time, nitrogen was used to fully replace the air in the reactor. Then, the temperature was slowly raised to 120° C. in a nitrogen atmosphere, the nitrogen flow rate was 150 mL / min, and the mixture was stirred at a constant temperature for 3 hours to obtain a diol composition.

[0229] The diol composition was separated using a liquid chromatography apparatus to obtain a diol having a cyclic imide structure, the structural formula of which is shown in Formula II-b-2 below. The conversion rate of the reaction was calculated to be 97.8%.

[0230] 2. Preparation of cyclic imide diol modified PBS resin material

[0231] 34.62 g (0.2 mol) of the separated diol with a cyclic imide structure, 236 g (2 mol) of succinic acid, and 90 g (1.0 mol) of 1,4-butanediol were weighed and put into a reactor, stirred and heated to melt in nitrogen, 100 ppm of zinc acetate was added when the temperature reached 170°C, and the temperature was maintained at a negative pressure of -0.03 MPa for 3 hours; then the pressure was restored to normal, 90 g (1.0 mol) of 1,4-butanediol was added, 500 ppm of n-butyl titanate was added, and the temperature was raised to 230°C; the vacuum was slowly evacuated to 1-2 Torr, and vacuum polycondensation was carried out for 7.0 hours to obtain a cyclic imide diol-modified PBS resin material with a melt flow index of 20±5 g / 10 min.

[0232] Example 6

[0233] In this embodiment, a diol monomer having a cyclic imide structure is synthesized, and an imide diol-modified PBS is prepared based on the diol monomer.

[0234] 1. Synthesis of diols containing cyclic imide structures

[0235] 1681.1 g (10 mol) of 2-amino-1-phenyl-1,3-propanediol and 1180.1 g (10 mol) of 1,4-butanedioic acid after vacuum drying were put into a reactor, and 100 ppm each of triphenyl phosphite (thermal stabilizer) and tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentyl erythritol ester (antioxidant) were added (compared to the weight of the entire reaction system, the same below) and stirred at room temperature. At the same time, nitrogen was used to fully replace the air in the reactor. Then, the temperature was slowly raised to 120° C. in a nitrogen atmosphere, the nitrogen flow rate was 150 mL / min, and the mixture was stirred at a constant temperature for 3 hours to obtain a diol composition.

[0236] The diol composition was separated by liquid chromatography to obtain a diol having a cyclic imide structure, the structural formula of which is shown in Formula II-b-5 below. The conversion rate of the reaction was calculated to be 70.1%.

[0237] 2. Preparation of cyclic imide diol modified PBS resin material

[0238] 50.02 g (0.2 mol) of the separated diol with a cyclic imide structure, 236 g (2 mol) of succinic acid, and 90 g (1.0 mol) of 1,4-butanediol were weighed and put into a reactor, stirred and heated to melt in nitrogen, 100 ppm of zinc acetate was added when the temperature reached 170°C, and the temperature was maintained at a negative pressure of -0.03 MPa for 3 hours; then the pressure was restored to normal, 90 g (1.0 mol) of 1,4-butanediol was added, 500 ppm of n-butyl titanate was added, and the temperature was raised to 230°C; the vacuum was slowly evacuated to 1-2 Torr, and vacuum polycondensation was carried out for 5.5 hours to obtain a cyclic imide diol-modified PBS resin material with a melt flow index of 20±5 g / 10 min.

[0239] Example 7

[0240] In this embodiment, a diol monomer having a cyclic imide structure is synthesized, and an imide diol-modified PBS is prepared based on the diol monomer.

[0241] 1. Synthesis of diols containing cyclic imide structures

[0242] 911.1 g (10 mol) of 2-amino-1,3-propanediol and 1180.1 g (10 mol) of 1,4-butanedioic acid after vacuum drying were put into a reactor, and 100 ppm each of triphenyl phosphite (thermal stabilizer) and tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentyl erythritol ester (antioxidant) were added (compared to the weight of the entire reaction system, the same below) and stirred at room temperature. At the same time, nitrogen was used to fully replace the air in the reactor. Then, the temperature was slowly raised to 120° C. in a nitrogen atmosphere, the nitrogen flow rate was 150 mL / min, and the mixture was stirred at a constant temperature for 3 hours to obtain a diol composition.

[0243] The diol composition was separated by liquid chromatography to obtain a diol having a cyclic imide structure, the structural formula of which is shown in the following formula II-b-1. The conversion rate of the above reaction was calculated to be 98.5%.

[0244] 2. Preparation of cyclic imide diol modified PBS resin material

[0245] 17.31 g (0.1 mol) of the separated diol with a cyclic imide structure, 236 g (2 mol) of succinic acid, and 99 g (1.1 mol) of 1,4-butanediol were weighed and put into a reactor, stirred and heated to melt in nitrogen, 100 ppm of zinc acetate was added when the temperature reached 170°C, and the temperature was maintained at a negative pressure of -0.03 MPa for 3 hours; then the pressure was restored to normal, 90 g (1.0 mol) of 1,4-butanediol was added, 500 ppm of n-butyl titanate was added, and the temperature was raised to 230°C; the vacuum was slowly evacuated to 1-2 Torr, and vacuum polycondensation was carried out for 6.0 hours to obtain a cyclic imide diol-modified PBS resin material with a melt flow index of 20±5 g / 10 min.

[0246] Example 8

[0247] In this embodiment, a diol monomer having a cyclic imide structure is synthesized, and an imide diol-modified PBS is prepared based on the diol monomer.

[0248] 1. Synthesis of diols containing cyclic imide structures

[0249] 911.1 g (10 mol) of 2-amino-1,3-propanediol and 1180.1 g (10 mol) of 1,4-butanedioic acid after vacuum drying were put into a reactor, and 100 ppm each of triphenyl phosphite (thermal stabilizer) and tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentyl erythritol ester (antioxidant) were added (compared to the weight of the entire reaction system, the same below) and stirred at room temperature. At the same time, nitrogen was used to fully replace the air in the reactor. Then, the temperature was slowly raised to 120° C. in a nitrogen atmosphere, the nitrogen flow rate was 150 mL / min, and the mixture was stirred at a constant temperature for 3 hours to obtain a diol composition.

[0250] The diol composition was separated by liquid chromatography to obtain a diol having a cyclic imide structure, the structural formula of which is shown in the following formula II-b-1. The conversion rate of the above reaction was calculated to be 98.5%.

[0251] 2. Preparation of cyclic imide diol modified PBS resin material

[0252] 51.93 g (0.3 mol) of the separated diol with a cyclic imide structure, 236 g (2 mol) of succinic acid, and 81 g (0.9 mol) of 1,4-butanediol were weighed and put into a reactor, stirred and heated to melt in nitrogen, 100 ppm of zinc acetate was added when the temperature reached 170°C, and the temperature was maintained at a negative pressure of -0.03 MPa for 3 hours; then the pressure was restored to normal, 90 g (1.0 mol) of 1,4-butanediol was added, 500 ppm of n-butyl titanate was added, and the temperature was raised to 230°C; the vacuum was slowly evacuated to 1-2 Torr, and vacuum polycondensation was carried out for 7.0 hours to obtain a cyclic imide diol-modified PBS resin material with a melt flow index of 20±5 g / 10 min.

[0253] Example 9

[0254] In this embodiment, a diol monomer having a cyclic imide structure is synthesized, and an imide diol-modified PBS is prepared based on the diol monomer.

[0255] 1. Synthesis of diols containing cyclic imide structures

[0256] 911.1 g (10 mol) of 2-amino-1,3-propanediol and 1180.1 g (10 mol) of 1,4-butanedioic acid after vacuum drying were put into a reactor, and 100 ppm each of triphenyl phosphite (thermal stabilizer) and tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentyl erythritol ester (antioxidant) were added (compared to the weight of the entire reaction system, the same below) and stirred at room temperature. At the same time, nitrogen was used to fully replace the air in the reactor. Then, the temperature was slowly raised to 120° C. in a nitrogen atmosphere, the nitrogen flow rate was 150 mL / min, and the mixture was stirred at a constant temperature for 3 hours to obtain a diol composition.

[0257] The diol composition was separated by liquid chromatography to obtain a diol having a cyclic imide structure, the structural formula of which is shown in the following formula II-b-1. The conversion rate of the above reaction was calculated to be 98.5%.

[0258] 2. Preparation of cyclic imide diol modified PBS resin material

[0259] 69.24 g (0.4 mol) of the separated diol with a cyclic imide structure, 236 g (2 mol) of succinic acid, and 72 g (0.8 mol) of 1,4-butanediol were weighed and put into a reactor, stirred and heated to melt in nitrogen, 100 ppm of zinc acetate was added when the temperature reached 170°C, and the temperature was maintained at a negative pressure of -0.03 MPa for 3 hours; then the pressure was restored to normal, 90 g (1.0 mol) of 1,4-butanediol was added, 500 ppm of n-butyl titanate was added, and the temperature was raised to 230°C; the vacuum was slowly evacuated to 1-2 Torr, and vacuum polycondensation was carried out for 8.0 hours to obtain a cyclic imide diol-modified PBS resin material with a melt flow index of 20±5 g / 10 min.

[0260] Example 10

[0261] In this embodiment, a diol monomer having a cyclic imide structure is synthesized, and imide diol-modified PET is prepared based on the diol monomer.

[0262] 1. Synthesis of diols containing cyclic imide structures

[0263] 911.1 g (10 mol) of 2-amino-1,3-propanediol and 1180.1 g (10 mol) of 1,4-butanedioic acid after vacuum drying were put into a reactor, and 100 ppm each of triphenyl phosphite (thermal stabilizer) and tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentyl erythritol ester (antioxidant) were added (compared to the weight of the entire reaction system, the same below) and stirred at room temperature. At the same time, nitrogen was used to fully replace the air in the reactor. Then, the temperature was slowly raised to 120° C. in a nitrogen atmosphere, the nitrogen flow rate was 150 mL / min, and the mixture was stirred at a constant temperature for 3 hours to obtain a diol composition.

[0264] The diol composition was separated by liquid chromatography to obtain a diol having a cyclic imide structure, the structural formula of which is shown in the following formula II-b-1. The conversion rate of the above reaction was calculated to be 98.5%.

[0265] 2. Preparation of cyclic imide diol modified PET resin material

[0266] 34.62 g (0.2 mol) of the separated diol having a cyclic imide structure, 332.2 g (2 mol) of terephthalic acid, and 62 g (1.0 mol) of ethylene glycol were weighed and placed in a reaction kettle. The mixture was stirred and heated to melt in nitrogen. When the temperature reached 170° C., 100 ppm of zinc acetate was added. The temperature was maintained at a pressure of 300 kPa and the reaction was continued until the distillate reached 97% of the theoretical water output. The pressure was then slowly restored to normal, and 62 g (1.0 mol) of ethylene glycol and 500 ppm of n-butyl titanate were added. The temperature was raised to 230° C. The mixture was slowly evacuated to 1-2 Torr and vacuum polycondensed for 4 hours to obtain a cyclic imide diol-modified PET resin material having a melt flow index of 20±5 g / 10 min.

[0267] Example 11

[0268] In this embodiment, a diol monomer having a cyclic imide structure is synthesized, and an imide diol-modified PBA is prepared based on the diol monomer.

[0269] 1. Synthesis of diols containing cyclic imide structures

[0270] 911.1 g (10 mol) of 2-amino-1,3-propanediol and 1180.1 g (10 mol) of 1,4-butanedioic acid after vacuum drying were put into a reactor, and 100 ppm each of triphenyl phosphite (thermal stabilizer) and tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentyl erythritol ester (antioxidant) were added (compared to the weight of the entire reaction system, the same below) and stirred at room temperature. At the same time, nitrogen was used to fully replace the air in the reactor. Then, the temperature was slowly raised to 120° C. in a nitrogen atmosphere, the nitrogen flow rate was 150 mL / min, and the mixture was stirred at a constant temperature for 3 hours to obtain a diol composition.

[0271] The diol composition was separated by liquid chromatography to obtain a diol having a cyclic imide structure, the structural formula of which is shown in the following formula II-b-1. The conversion rate of the above reaction was calculated to be 98.5%.

[0272] 2. Preparation of cyclic imide diol modified PBA resin material

[0273] 34.62 g (0.2 mol) of the separated diol with a cyclic imide structure, 192.2 g (2 mol) of 1,6-hexanediol, and 90 g (1.0 mol) of butanediol were weighed and put into a reactor, stirred and heated to melt in nitrogen, 100 ppm of zinc acetate was added when the temperature reached 170°C, and the temperature was maintained at a negative pressure of -0.03 MPa for 3 hours; then the pressure was restored to normal, 90 g (1.0 mol) of ethylene glycol was added, 500 ppm of n-butyl titanate was added, and the temperature was raised to 230°C; the vacuum was slowly evacuated to 1-2 Torr, and vacuum polycondensation was performed for 8.0 hours to obtain a cyclic imide diol-modified PBA resin material with a melt flow index of 20±5 g / 10 min.

[0274] Example 12

[0275] In this embodiment, a diol monomer having a cyclic imide structure is synthesized, and an imide diol-modified PBS is prepared based on the diol monomer.

[0276] 1. Synthesis of diols containing cyclic imide structures

[0277] 911.1 g (10 mol) of 2-amino-1,3-propanediol and 1180.1 g (10 mol) of 1,4-butanedioic acid after vacuum drying were put into a reactor, and 100 ppm each of triphenyl phosphite (thermal stabilizer) and tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentyl erythritol ester (antioxidant) were added (compared to the weight of the entire reaction system, the same below) and stirred at room temperature. At the same time, nitrogen was used to fully replace the air in the reactor. Then, the temperature was slowly raised to 120° C. in a nitrogen atmosphere, the nitrogen flow rate was 150 mL / min, and the mixture was stirred at a constant temperature for 3 hours to obtain a diol composition.

[0278] The diol composition was separated by liquid chromatography to obtain a diol having a cyclic imide structure, the structural formula of which is shown in the following formula II-b-1. The conversion rate of the above reaction was calculated to be 98.5%.

[0279] 2. Preparation of cyclic imide diol modified PBS resin material

[0280] 34.62 g (0.2 mol) of the separated diol with a cyclic imide structure, 236 g (2 mol) of succinic acid, and 90 g (1.0 mol) of 1,4-butanediol were weighed and put into a reactor, stirred and heated to melt in nitrogen, 100 ppm of zinc acetate was added when the temperature reached 170°C, and the temperature was kept to react for 3 hours under a negative pressure of -0.03 MPa; then the pressure was restored to normal, 90 g (1.0 mol) of 1,4-butanediol was added, 500 ppm of n-butyl titanate was added, and the temperature was raised to 230°C; the vacuum was slowly evacuated to 1-2 Torr, and vacuum polycondensation was carried out for 12.0 hours to obtain a cyclic imide diol-modified PBS resin material with a melt flow index of 10±2 g / 10 min.

[0281] Example 13

[0282] In this embodiment, a diol monomer having a cyclic imide structure is synthesized, and an imide diol-modified PBS is prepared based on the diol monomer.

[0283] 1. Synthesis of diols containing cyclic imide structures

[0284] 911.1 g (10 mol) of 2-amino-1,3-propanediol and 1180.1 g (10 mol) of 1,4-butanedioic acid after vacuum drying were put into a reactor, and 100 ppm each of triphenyl phosphite (thermal stabilizer) and tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentyl erythritol ester (antioxidant) were added (compared to the weight of the entire reaction system, the same below) and stirred at room temperature. At the same time, nitrogen was used to fully replace the air in the reactor. Then, the temperature was slowly raised to 120° C. in a nitrogen atmosphere, the nitrogen flow rate was 150 mL / min, and the mixture was stirred at a constant temperature for 3 hours to obtain a diol composition.

[0285] The diol composition was separated by liquid chromatography to obtain a diol having a cyclic imide structure, the structural formula of which is shown in the following formula II-b-1. The conversion rate of the above reaction was calculated to be 98.5%.

[0286] 2. Preparation of cyclic imide diol modified PBS resin material

[0287] 34.62 g (0.2 mol) of the separated diol with a cyclic imide structure, 236 g (2 mol) of succinic acid, and 90 g (1.0 mol) of 1,4-butanediol were weighed and put into a reactor, stirred and heated to melt in nitrogen, 100 ppm of zinc acetate was added when the temperature reached 170°C, and the temperature was maintained at a negative pressure of -0.03 MPa for 3 hours; then the pressure was restored to normal, 90 g (1.0 mol) of 1,4-butanediol was added, 500 ppm of n-butyl titanate was added, and the temperature was raised to 230°C; the vacuum was slowly evacuated to 1-2 Torr, and vacuum polycondensation was carried out for 5.0 hours to obtain a cyclic imide diol-modified PBS resin material with a melt flow index of 50±2 g / 10 min.

[0288] Comparative Example 1

[0289] In this comparative example, a diol monomer having a cyclic imide structure is synthesized, and an imide diol-modified PBS is prepared based on the diol monomer.

[0290] 1. Synthesis of diols containing cyclic imide structures

[0291] The synthesis process and parameters for this comparative example were the same as those for Example 2, except that 911.1 g (10 mol) of 2-amino-1,3-propanediol and 1601.7 g (10 mol) of 1,7-heptanedioic acid were used to synthesize a diol containing a cyclic imide structure. The resulting diol having a cyclic imide structure has the structural formula shown in Formula II-e-1 below, and the calculated conversion rate of the reaction was 24.8%.

[0292] 2. Preparation of cyclic imide diol modified PBS resin material

[0293] The synthesis process and parameters of this comparative example are the same as those of Example 2, except that the vacuum polycondensation in this comparative example is 8.0 h; a cyclic imide diol-modified PBS resin material having a melt flow index of 150±5 g / 10 min is obtained.

[0294] Comparative Example 2

[0295] In this comparative example, a diol monomer having a cyclic imide structure is synthesized, and an imide diol-modified PBS is prepared based on the diol monomer.

[0296] 1. Synthesis of diols containing cyclic imide structures

[0297] The synthesis process and parameters for this comparative example were the same as those for Example 2, except that 911.1 g (10 mol) of 2-amino-1,3-propanediol and 1741.4 g (10 mol) of 1,8-octanedioic acid were used to synthesize a diol containing a cyclic imide structure. The resulting diol having a cyclic imide structure has the structural formula shown in Formula II-f-1 below, and the calculated conversion rate of the reaction was 13.3%.

[0298] 2. Preparation of cyclic imide diol modified PBS resin material

[0299] The synthesis process and parameters of this comparative example are the same as those of Example 2, except that: this comparative example is vacuum polycondensed for 8.0 hours to obtain a cyclic imide diol-modified PBS resin material with a melt flow index of 150±5 g / 10 min.

[0300] Comparative Example 3

[0301] In this comparative example, a diol monomer having a cyclic imide structure is synthesized, and an imide diol-modified PBS is prepared based on the diol monomer.

[0302] 1. Synthesis of diols containing cyclic imide structures

[0303] The synthesis process and parameters for this comparative example were the same as those for Example 2, except that 911.1 g (10 mol) of 2-amino-1,3-propanediol and 1881.4 g (10 mol) of 1,9-nonedioic acid were used to synthesize a diol containing a cyclic imide structure. The resulting diol having a cyclic imide structure has the structural formula shown in Formula II-g-1 below, and the conversion rate of the reaction was calculated to be 10.6%.

[0304] 2. Preparation of cyclic imide diol modified PBS resin material

[0305] The synthesis process and parameters of this comparative example are the same as those of Example 2, except that: this comparative example is vacuum polycondensed for 8.0 hours to obtain a cyclic imide diol-modified PBS resin material with a melt flow index of 150±5 g / 10 min.

[0306] Comparative Example 4

[0307] In this comparative example, a PBS resin material was prepared as follows: 236 g (2 mol) of succinic acid and 108 g (1.2 mol) of 1,4-butanediol were weighed and put into a reactor, stirred and heated to melt in nitrogen, 100 ppm of zinc acetate was added when the temperature reached 170°C, and the temperature was maintained at a negative pressure of -0.03 MPa for 3 hours; then the pressure was restored to normal, 90 g (1.0 mol) of 1,4-butanediol was added, 500 ppm of n-butyl titanate was added, and the temperature was raised to 230°C; the pressure was slowly evacuated to 1-2 Torr, and vacuum polycondensation was performed for 9.0 hours to obtain a non-modified PBS resin material with a melt flow index of 20±5 g / 10 min.

[0308] Comparative Example 5

[0309] In this comparative example, a diol monomer having a cyclic imide structure is synthesized, and an imide diol-modified PBS is prepared based on the diol monomer.

[0310] 1. Synthesis of diols containing cyclic imide structures

[0311] The synthesis process and parameters of this comparative example are the same as those of Example 2.

[0312] 2. Preparation of cyclic imide diol modified PBS resin material

[0313] 173.1 g (1 mol) of the separated diol with a cyclic imide structure and 236 g (2 mol) of succinic acid were weighed and put into a reactor, stirred and heated to melt in nitrogen, 100 ppm of zinc acetate was added when the temperature reached 170°C, and the temperature was maintained at a negative pressure of -0.03 MPa for 3 hours; then the pressure was restored to normal, 108 g (1.2 mol) of 1,4-butanediol was added, 500 ppm of n-butyl titanate was added, and the temperature was raised to 230°C; the vacuum was slowly evacuated to 1-2 Torr, and vacuum polycondensation was performed for 6.5 hours to obtain a cyclic imide diol-modified PBS resin material with a melt flow index of 120±5 g / 10 min.

[0314] Comparative Example 6

[0315] In this comparative example, a diol monomer having a cyclic imide structure is synthesized, and an imide diol-modified PBS is prepared based on the diol monomer.

[0316] 1. Synthesis of diols containing cyclic imide structures

[0317] The synthesis process and parameters of this comparative example are the same as those of Example 2.

[0318] 2. Preparation of cyclic imide diol modified PBS resin material

[0319] The synthesis process and parameters of this comparative example are the same as those of Example 2, except that the vacuum polycondensation in this comparative example is 4 hours to obtain a cyclic imide diol-modified PBS resin material with a melt flow index of 150±5 g / 10 min.

[0320] Comparative Example 7

[0321] In this embodiment, a one-step one-pot method is used to synthesize a diol monomer having a cyclic imide structure, and an imide diol-modified PBS is prepared based on the diol monomer.

[0322] 36.4 g (0.4 mol) of 2-amino-1,3-propanediol, 236.0 g (2 mol) of 1,4-butanediol and 180.2 g (2 mol) of 1,4-butanediol after vacuum drying were put into a reactor, and 100 ppm of triphenyl phosphite (heat stabilizer) and 100 ppm of tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]pentyl erythritol (antioxidant) were added at the same time. The mixture was stirred at room temperature and the air in the reactor was fully replaced with nitrogen. The temperature was then slowly raised to 120°C in a nitrogen atmosphere. ℃, nitrogen flow rate 150mL / min, and constant temperature stirring until no more distillate increases; continue stirring and heat to 170℃, add 100ppm zinc acetate, and keep the temperature to react at a negative pressure of -0.03MPa for 3h; then return to normal pressure, add 500ppm n-butyl titanate, and heat to 230℃; slowly evacuate to 1-2Torr, and vacuum polycondense until its melt flow index no longer decreases, finally obtaining a cyclic imide diol-modified PBS resin material with a melt flow index of 142g / 10min.

[0323] Test example

[0324] The tensile strength, elastic modulus, and elongation at break of the resin materials obtained in the Examples and Comparative Examples were tested in accordance with GB / T 1040.2-2006. The glass transition temperature (Tg) and melting temperature (Tm) of the resin materials obtained in the Examples and Comparative Examples were tested in accordance with GB / T 19466.2-2004. The melt flow index (MFI) was tested in accordance with ASTM D1238-2010.

[0325] The relevant synthetic data and test performance are summarized. For specific parameters, please see the table below.

[0326] discuss

[0327] Referring to Examples 1 to 4, the preparation of diols with cyclic imide structures exhibited relatively excellent yields. By extending the reaction time, the synthesis yield could be increased to over 80%. Furthermore, the mechanical properties (tensile strength) of the polyester materials prepared in Examples 1 to 4 were superior to those of Comparative Example 4 (i.e., a conventional polyester material). Referring to Examples 2, 7 to 9, and Comparative Example 5, the mechanical properties of the resulting polyester materials gradually decreased with increasing molar proportion of the cyclic imide diol in the total diol monomers. It can be inferred that the enhanced mechanical properties of the modified monomers on the main polymer are achieved without affecting the main polymer structure and crystallization characteristics. Specifically, the mechanical properties of the polyester materials prepared in Examples 7 and 8 (with a 15% modification ratio) were still superior to those of Comparative Example 4 (i.e., a conventional polyester material). Referring to Examples 2, 12 to 13, and Comparative Example 6, under the assumption that reaction conditions such as temperature remained unchanged, the melt flow index of the modified resin decreased with increasing reaction time, and the mechanical properties of the resulting polyester materials gradually improved. Referring to Example 2, Comparative Example 6 and Comparative Example 7, based on the similar addition ratio of the modified monomers, by first synthesizing the modified composition and then polymerizing it, the "step-by-step method" and the "one-step one-pot method" are compared. It can be seen that the block polymer obtained by the "step-by-step method" is easier to prepare a modified polymer with high molecular weight, excellent thermal properties and mechanical properties than the mixed polymer obtained by the "one-step method".

[0328] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any appropriate manner without contradiction. To avoid unnecessary repetition, the present invention will not further describe various possible combinations.

Claims

1. A copolymer comprising a polymer main structural unit and a structural unit for improving polymer strength, The structural unit side chain group for improving the polymer strength contains an imide ring structure (R-0): Preferably, the structural unit for improving the strength of the polymer contains an imide ring structure represented by (RI); Also preferably, the structural unit for improving the strength of the polymer further contains an open-ring structure of the imide represented by (R-I'): X1 and X2 are O or N; R1 is a residue of an easily cyclized dibasic acid, preferably an alkylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl, an alkylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl and is interrupted by one or more O atoms, an alkenylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a cycloalkylene group or a heterocycloalkyl group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a cycloalkenylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, an arylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a heteroarylene group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, or a bridged ring group which is unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro; Preferably, the alkylene group in the definition of R1 is C1-C 10 The alkylene group is preferably a C1-C6 alkylene group, more preferably a C1-C5 alkylene group, and most preferably a methylene group, an ethylene group, a 1-methylethylene group, a 1,1-dimethylethylene group, a 1,2-dimethylethylene group, a 1,1,2,2-tetramethylethylene group, a 1-phenylethylene group, a 1-benzylethylene group, a 1,1-diphenylethylene group, a 1,1-dibenzylethylene group, a 1,2-diphenylethylene group, a 1,2-dibenzylethylene group, a propylene group, a 1-methylpropylene group, a 2-methylpropylene group, a 1,1-dimethylpropylene group, a 1,2-dimethylpropylene group, a 2,2-dimethylpropylene group, a 1,3-dimethylpropylene group, a 1-phenylpropylene group, a 2-phenylpropylene group, a 1,2-diphenylpropylene group, a 2,2-diphenylpropylene group, or a 1,3-diphenylpropylene group; the alkenylene group in the definition of R1 is a C2-C6 alkylene group, more preferably a C1-C5 alkylene group, and most preferably a methylene group, an ethylene group, a 1-methylethylene group, a 1,1-dimethylethylene group, a 1,2-dimethylpropylene group, a 2,2-diphenylpropylene group, a 2,2-diphenylpropylene group, or a 1,3-diphenylpropylene group. 10 The alkenylene group is preferably a C2-C6 alkenylene group, more preferably a C2-C3 alkenylene group, and most preferably vinylene, 1-methylvinylene, 1,2-dimethylvinylene or propenylene group; the alkylene group in the definition of R1, which is unsubstituted or substituted by a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl, is interrupted by 1-3 oxygen atoms, such as 2-oxa-1,3-ethylene; the cycloalkylene group in the definition of R1 is a C3-C8 cycloalkylene group, preferably a C4-C6 cycloalkylene group, and most preferably a cyclobutylene or cyclohexylene group; the cycloalkenylene group in the definition of R1 can be a C4-C8 cycloalkenylene group, preferably a C4-C6 cycloalkenylene group, and most preferably a 3-cyclohexene-1,6-diyl group; the arylene group in the definition of R1 is a C6-C 10 Arylene is preferably phenylene, such as 1,6-phenylene; the bridging ring group in the definition of R1 is norbornene; R2 is a residue of a diol containing an amino group, preferably a trivalent alkyl group which is unsubstituted or substituted with a substituent selected from a halogen, an alkyl group or a nitro group, or at least one of a trivalent alkyl-aryl-alkyl group which is unsubstituted or substituted with a substituent selected from a halogen, an alkyl group or a nitro group; Preferably, the trivalent alkyl-aryl-alkyl group in the definition of R2 is a trivalent C1-C 10 Alkyl-C6-C 10 Aryl-C1-C 10 Alkyl, preferably a trivalent C1-C5 alkyl-C6-C8 aryl-C1-C5 alkyl, more preferably a trivalent C1-C3 alkyl-C6-C8 aryl-C1-C3 alkyl, Preferably, R2 is selected from at least one of the following structures: In the above formula, * represents the connection site with the O atom, and ** represents the connection site with the N atom; Further preferably: R1 is selected from an alkylene group having 1 to 7 carbon atoms, preferably a straight or branched alkylene group having 1, 2, 3 or 4 carbon atoms in the main chain, an arylene group having 6 to 12 carbon atoms, a heteroarylene group having 5 to 11 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, a heterocycloalkylene group having 2 to 11 carbon atoms or a combination thereof, optionally containing the following substituents: halogen, nitro, C 1-4 Alkyl, halogenated C 1-4 Alkyl, C 6-12 Aryl, C 6-12 Aryl-C 1-4 Alkyl or halogenated, C 1-4 Alkyl substituted C 6-12 Aryl or C 6-12 Aryl-C 1-4 alkyl; R2 is selected from a linear alkylene group having 2 to 12 carbon atoms, a branched alkylene group having 3 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms, a cycloalkylene group having 3 to 12 carbon atoms, or a trivalent C1-C5 alkyl-C6-C8 aryl-C1-C5 alkyl group, optionally containing the following substituents: halogen, nitro, C 1-4 Alkyl, halogenated C 1-4 Alkyl, C 6-12 Aryl, C 6-12 Aryl-C 1-4 Alkyl or halogenated, C 1-4 Alkyl substituted C 6-12 Aryl or C 6-12 Aryl-C 1-4 alkyl; Most preferably: R1 is a straight chain alkylene group having 2 or 3 carbon atoms in the main chain; R2 is selected from a straight chain alkylene group having 2 to 12 carbon atoms, a branched chain alkylene group having 3 to 12 carbon atoms, a trivalent C1-C3 alkyl-C6-C8 aryl-C1-C3 alkyl group, an aryl group having 6 to 12 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms.

2. The copolymer according to claim 1, wherein the copolymer is at least one of a random copolymer, an alternating copolymer, a block copolymer and a graft copolymer of a main chain structural unit and a structural unit for improving polymer strength, preferably a random copolymer and / or a block copolymer.

3. The copolymer according to claim 1, wherein the structural unit containing the (RI) structure for improving the polymer strength is polyester, polyamide, polyurethane, polycarbonate or polyurea; Preferably, it has the following structure: X3 and X4 are N or O; R3 is any divalent organic group; Preferably, it is a residue of a dicarboxylic acid used for polymer synthesis, and is different from R1 and is a residue of any dicarboxylic acid, for example, it is a residue of an easily cyclizable dicarboxylic acid as described in R1; or R3 is a residue of a dicarboxylic acid that is not easily cyclizable, and the dicarboxylic acid that is not easily cyclizable may be, for example, terephthalic acid or sebacic acid; Preferably, R3 is a chemical bond or an alkylene group that is unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl, and an alkylene group that is unsubstituted or substituted with a substituent selected from halogen, alkyl, aryl, arylalkyl or alkylaryl with one or more O atoms. at least one of an alkylene group substituted with a substituent selected from halogen, alkyl or nitro, an alkenylene group unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a cycloalkylene group unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a cycloalkenylene group unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, an arylene group unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, a heteroarylene group unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro, or a bridged ring group unsubstituted or substituted with a substituent selected from halogen, alkyl or nitro; Preferably, R3 is selected from a linear or branched alkylene or alkenylene group having 2 to 12 carbon atoms, optionally interrupted by O atoms, an arylene group having 6 to 12 carbon atoms, a heteroarylene group having 5 to 11 carbon atoms, a cycloalkylene group, a cycloalkenyl group or a bridged cycloalkyl group having 3 to 12 carbon atoms, a heterocycloalkylene group having 2 to 11 carbon atoms, or a combination of the above groups, optionally containing the following substituents: halogen, C 1-4 Alkyl, halogenated C 1-4 Alkyl, C 6-12 Aryl, C 6-12 Aryl-C 1-4 Alkyl or halogenated, C 1-4 Alkyl substituted C 6-12 Aryl or C 6-12 Aryl-C 1-4 alkyl.

4. The copolymer according to claim 3, wherein the structural unit containing (RI) is a polyester unit; R1, R2 or R3 is as described in claim 1 or 3.

5. The copolymer according to claim 1, wherein the main structural unit is polyester, polyamide, polycarbonate, polyurethane or polyurea; Preferably, the main structural unit is a polyester such as one or more of aliphatic polyester, aliphatic-aromatic polyester, and aromatic polyester; further preferably, the main structural unit comprises two or more different structural units; Preferably, it is a structural unit of one or more polyesters selected from PBS, PES, PBA, PET, PBT, PTT, PBAT, PBST, PEAT or PEST; Preferably, the main structural unit of the copolymer and the structural unit for improving the strength of the polymer are both polyesters; Preferably, R1 in the structural unit that improves the strength of the polymer is 3, i.e., 1,5-glutaric acid forms an imide heterocycle; Preferably, R1 in the structural unit that improves the strength of the polymer is 2, that is, 1,4-succinic acid forms an imide heterocycle; preferably, the melt flow index of the copolymer is less than 130g / 10min, less than 100g / 10min, less than 80g / 10min, less than 50g / 10min, less than 20g / 10min, less than 15g / 10min, according to ASTM-D1238 standard.

6. The copolymer according to claim 5, characterized in that The molar ratio of the structural unit for improving polymer strength to the main structural unit is 0.01 to 2.34, preferably 0.01 to 0.

25.

7. The copolymer according to claim 1, further comprising other modified structural units.

8. A polymer alloy comprising the copolymer according to any one of claims 1 to 7.

9. A polymer composition or a molded article comprising the copolymer according to any one of claims 1 to 7 or the polymer alloy according to claim 8.

10. Use of the copolymer according to any one of claims 1 to 7, the copolymer alloy according to claim 8, or the composition or molded body according to claim 9 for food containers, food packaging films, disposable tableware such as spoons or straws, packaging containers such as transparent boxes for daily necessities, cosmetics, and household appliances, transparent windows for cartons, transparent folders, stationery such as document holders, industrial films or agricultural films, and chemical fibers for clothing or industry.

11. Use of a diol monomer represented by formula (II), a diol monomer containing an amide bond represented by formula (I), a precursor composition of a monomer represented by formula II or formula I, or a prepolymer formed by a monomer represented by formula II or I and a dicarboxylic acid for polymer synthesis (e.g., a carboxyl-terminated prepolymer or a hydroxyl-terminated prepolymer) in the preparation of a copolymer with improved strength; preferably, the tensile strength of the copolymer with improved strength is higher than 30 MPa; The diol monomer represented by formula (II) is: The diol monomer containing an amide bond shown in formula (I) is: R1 and R2 are as defined in claim 1; The precursor composition of the monomer of formula (II) or formula (I) is a primary amino diol and an easily cyclic dibasic acid and / or an acid anhydride corresponding to the dibasic acid, or a diol monomer containing an amide bond, wherein the primary amino diol is HOR2(NH2)OH.

12. A method for preparing a copolymer, characterized in that: include: A monomer composition is obtained by subjecting a primary amino diol to a cyclization reaction with a dibasic acid and / or an acid anhydride corresponding thereto to generate an imide; The monomer composition is subjected to an esterification / transesterification reaction with a diol and a dibasic acid / ester to obtain a polyester copolymer containing a segment for improving polymer strength as shown in formula (III); The chain segment for improving polymer strength has a structure shown in formula (III): Wherein, m is any integer from 1 to 150; In the formula, R1 and R2 have the meanings as defined in claim 1, and R3 has the definition as defined in claim 3.

13. The preparation method according to claim 12, characterized in that: The dibasic acid / ester is selected from one or more of aromatic dibasic acid / ester and aliphatic dibasic acid / ester.

14. The preparation method according to claim 12, characterized in that: The structural formula of the primary amino diol is shown in formula (IV): In the formula, R2 is as defined in claim 1; Preferably, the primary amino diol is one or more of 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-1-phenyl-1,3-propanediol, 4-amino-1,2-butanediol or 3,4-dihydroxyaniline.

15. The preparation method according to claim 12, characterized in that: The dibasic acid is a fatty carboxyl-terminated dibasic acid having 3-9 carbon atoms; more preferably, it is a straight-chain or branched fatty carboxyl-terminated dibasic acid having 4-6 main chain carbon atoms.

16. The preparation method according to claim 12, characterized in that: The monomer composition includes a diol monomer containing an imide cyclic structure; The structural formula of the diol monomer containing an imide ring structure is shown in formula (II): wherein R1 and R2 are as defined in claim 1.

17. The preparation method according to claim 12, characterized in that: The monomer composition comprises a diol monomer containing an imide ring structure, a primary amino diol and / or a dibasic acid and / or an acid anhydride raw material corresponding to the dibasic acid, a diol monomer containing an amide bond, and a polyester prepolymer; The structural formula of the diol monomer containing an imide ring structure is shown in formula (II): wherein R1 and R2 are as defined in claim 1.

18. The preparation method according to claim 17, characterized in that: The structural formula of the diol monomer containing an amide bond is shown in formula (I): wherein R1 and R2 are as defined in claim 1.

19. The preparation method according to claim 17, characterized in that: The polyester prepolymer is a carboxyl-terminated prepolymer obtained by reacting a diol monomer containing an imide ring structure and / or a primary amino diol and / or a diol monomer containing an amide bond with an excess of a dibasic acid; or The polyester prepolymer is a hydroxyl-terminated prepolymer obtained by reacting an excessive amount of a diol monomer containing an imide ring structure and / or a primary amino diol and / or a diol monomer containing an amide bond with a dibasic acid.

20. The preparation method according to claim 12, characterized in that: The molar ratio of the primary amino diol to the dibasic acid and / or the acid anhydride corresponding thereto is 1:1.01-1:6.

00.

21. The preparation method according to claim 12, characterized in that: The cyclization reaction to generate the imide comprises: Adding primary amino diol and dibasic acid together, stirring and mixing, heating and melting, and performing an amidation reaction to obtain a diol containing an amide bond as shown in formula (I); The diol containing an amide bond is continuously stirred and kept warm under hot conditions to undergo a thermal cyclization reaction, thereby obtaining a molten mixed solution containing a diol containing an imide cyclic structure as shown in formula (II), i.e., a monomer composition; wherein R1 and R2 are as defined in claim 1.

22. The preparation method according to claim 21, characterized in that: The amidation reaction is carried out in a dry inert atmosphere that has been replaced with air, and a heat stabilizer and an antioxidant are added together with the primary amino diol and the dibasic acid; Preferably, the thermal cyclization reaction temperature is 80-190° C., and the reaction time is 0.5-6 h.

23. The preparation method according to claim 21, characterized in that: The thermal cyclization reaction is carried out under an inert atmosphere; preferably, the inert gas is nitrogen, and the flow rate of nitrogen in the thermal cyclization reaction system is >100 mL / min.

24. The preparation method according to claim 17, characterized in that: The total molar proportion of the polyester prepolymer obtained by reacting the diol monomer containing an imide ring structure and the diol monomer containing an amide bond in the monomer composition exceeds 80%, preferably exceeds 90%, and more preferably exceeds 95%.

25. A polyester, wherein the polyester is polymerized from dicarboxylic acid and diol monomers, the side chain groups of some diol monomer fragments contain cycloheximide groups, and the melt flow index of the polyester is less than 130 g / 10 min according to ASTM-D1238 standard.

26. A polyester, wherein the polyester is polymerized from dicarboxylic acid and diol monomers, the side chain groups of some diol monomer fragments contain cyclopentaneimide groups, and the melt flow index of the polyester is less than 130 g / 10 min in accordance with ASTM-D1238 standard.

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